Method for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded article

文档序号：213923 发布日期：2021-11-05 浏览：17次中文

阅读说明：本技术 聚碳酸酯共聚物和聚硅氧烷化合物的制造方法、聚碳酸酯共聚物、聚硅氧烷化合物、组合物以及成型体 (Method for producing polycarbonate copolymer and polysiloxane compound, polycarbonate copolymer, polysiloxane compound, composition, and molded article ) 是由上等和良釜谷康平富田惠介秋元宣人于 2020-03-19 设计创作，主要内容包括：本发明提供有效地制造耐冲击性优异且熔融时的流动性高的具有硅氧烷结构单元的聚碳酸酯共聚物的方法等。还提供不产生酸等环境负荷高的副产物、并且能够在无溶剂、特别是无安全方面存在顾虑的溶剂的条件下实施的、有效地制造聚碳酸酯共聚物或聚硅氧烷化合物的方法、以及聚硅氧烷化合物等。该聚碳酸酯共聚物的制造方法具有在酯交换催化剂的存在下使选自规定的二芳氧基硅烷化合物、规定的二烷氧基硅烷和规定的硅化合物中的硅烷系化合物、碳酸酯化合物与包括芳香族二醇化合物或脂环式二醇化合物的二醇化合物聚合的聚合工序,在聚合工序中,以熔融状态在减压下边除去来自上述碳酸酯化合物的醇边制造具有式(1－1)～式(1－4)的任一式所示的硅氧烷结构单元和具有规定的聚碳酸酯结构单元的聚碳酸酯共聚物。通过该方法,上述技术问题得以解决。(式中,R～(1)～R～(10)、R～(30)～R～(33)、Z-(1)、Z-(2)、J-(1)、K-(1)、A-(1)、A-(2)、L-(1)、L-(2)和X如说明书的记载。)(The present invention provides a method for efficiently producing a polycarbonate copolymer having siloxane structural units, which is excellent in impact resistance and has high fluidity when melted. Also provided is a method for producing a solvent-free, particularly non-safe, by-product which does not generate an acid or the like and is highly environmentally friendlyA method for efficiently producing a polycarbonate copolymer or a polysiloxane compound, and a polysiloxane compound, which are carried out under a solvent condition where the solvent is concerned. The method for producing a polycarbonate copolymer comprises a polymerization step of polymerizing a silane compound or a carbonate compound selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane and a predetermined silicon compound with a diol compound comprising an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst, wherein a polycarbonate copolymer having a siloxane structural unit represented by any one of the formulae (1-1) to (1-4) and a predetermined polycarbonate structural unit is produced in the polymerization step while removing an alcohol derived from the carbonate compound in a molten state under reduced pressure. By this method, the above technical problem is solved. (in the formula, R 1 ～R 10 、R 30 ～R 33 、Z 1 、Z 2 、J 1 、K 1 、A 1 、A 2 、L 1 、L 2 And X is as described in the specification. ))

1. A method for producing a polycarbonate copolymer, characterized in that,

comprising a polymerization step of polymerizing a silane compound, a carbonate compound and a diol compound containing an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst,

the silane-based compound is selected from a diaryloxysilane compound, a dialkoxysilane compound, and a silicon compound, wherein the diaryloxysilane compound includes at least any one of a dialkyldiaryloxysilane, a diaryldiaryldiaryldiaryldiaryldiaryldiarylaryloxysilane, and a monoalkyl monoaryldiarylaryloxysilane, the dialkoxysilane compound includes at least any one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkyl monoaryldialkoxysilane, and the silicon compound includes at least one of a cyclic siloxane compound and a linear siloxane compound,

in the polymerization step, a polycarbonate copolymer having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4) is produced in a molten state under reduced pressure while removing an alcohol derived from the carbonate compound,

in the formulae (1-1) to (1-4), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

R³～R¹⁰and R³⁰～R³³Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted carbonAn aryl group having 6 to 30 atoms,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

in the formula (2), R¹¹And R¹²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R¹¹And R¹²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

a and b each independently represent 0 or an integer of 1 to 5000,

in the formulae (3-1) to (3-4), R¹³～R²⁰And R⁴⁰～R⁵¹Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

Z₃and Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

in the formula (4), R²¹And R²²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R²¹And R²²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

c and d each independently represent 0 or an integer of 1 to 5000.

2. The method for producing a polycarbonate copolymer according to claim 1,

Z₁～Z₄each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁and J₂Each independently represents an integer of 0 to 2 inclusive,

K₁and K₂Each independently represents an integer of 0 to 2.

3. The method for producing a polycarbonate copolymer according to claim 1 or 2,

said X has the presentation R¹¹And R¹²Siloxane structural units of a fluorene ring structure formed by bonding with each other, and/or Y has a structure representing R²¹And R²²Of fluorene ring structures bonded to each otherA polycarbonate structural unit.

4. A method for producing a polycarbonate copolymer, characterized in that,

in the polymerization step, a polycarbonate copolymer having a siloxane structural unit represented by formula (1) and a polycarbonate structural unit represented by formula (3) is produced in a molten state under reduced pressure while removing an alcohol derived from the carbonate compound,

in the formula (1), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

R³～R¹⁰each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000,

in the formula (3), R¹³～R²⁰Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

y is any one of structural formulas shown in a formula (4),

c and d each independently represent 0 or an integer of 1 to 5000.

5. The method for producing a polycarbonate copolymer according to any one of claims 1 to 4,

the transesterification catalyst comprises an alkali metal compound and/or an alkaline earth metal compound.

6. The method for producing a polycarbonate copolymer according to claim 5,

the alkali metal compound and/or alkaline earth metal compound comprises a carbonate.

7. The method for producing a polycarbonate copolymer according to any one of claims 1 to 6,

the weight average molecular weight of the polycarbonate copolymer is 10000-300000.

8. The method for producing a polycarbonate copolymer according to any one of claims 1 to 7,

in the polymerization step, the amount of the transesterification catalyst relative to the amount of the diol compound is 1.0 × 10 in terms of a molar ratio^－7～1.0×10^－2。

9. The method for producing a polycarbonate copolymer according to any one of claims 1 to 8,

the reaction temperature in the polymerization step is in the range of 150 ℃ to 300 ℃.

10. The method for producing a polycarbonate copolymer according to any one of claims 1 to 9,

the polymerization step further comprises a pressure reduction step of gradually reducing the reaction pressure to 400Pa or less.

11. The method for producing a polycarbonate copolymer according to any one of claims 1 to 10,

in the polymerization step, the carbonate compound and the diol compound are polymerized under a pressure of 400Pa or less.

12. The method for producing a polycarbonate copolymer according to any one of claims 1 to 11,

no solvent is used in the polymerization step.

13. The method for producing a polycarbonate copolymer according to any one of claims 1 to 12,

the ratio of the total number of moles of the carbonate compound and the diaryloxysilane compound used in the polymerization step to the number of moles of the diol compound is 0.9 to 1.2.

14. The method for producing a polycarbonate copolymer according to any one of claims 1 to 13,

the number of moles of the siloxane structural unit in the polycarbonate copolymer is 1-1000, and the number of moles of the polycarbonate structural unit is 1-1000.

15. The method for producing a polycarbonate copolymer according to any one of claims 1 to 14,

the molar ratio of the siloxane structural unit to the polycarbonate structural unit is 0.01: 99.99-99.99: 0.01.

16. The method for producing a polycarbonate copolymer according to any one of claims 1 to 15,

the polycarbonate copolymer has a Q value of 8X 10 as measured at 280 ℃ and 160kgf^－2cm³s^－1The above.

17. A polycarbonate copolymer characterized in that,

having a siloxane structural unit represented by any one of formulae (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulae (3-1) to (3-4), wherein the low molecular weight compound having a weight average molecular weight of 1000 or less is 30% by weight or less,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000,

Z₃and Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

c and d each independently represent 0 or an integer of 1 to 5000.

18. The polycarbonate copolymer of claim 17,

Z₁～Z₄each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁and J₂Each independently represents an integer of 0 to 2 inclusive,

K₁and K₂Each independently represents an integer of 0 to 2.

19. The polycarbonate copolymer of claim 17 or 18,

said X has the presentation R¹¹And R¹²Siloxane structural units of a fluorene ring structure formed by bonding with each other, and/or Y has a structure representing R²¹And R²²And a polycarbonate structural unit having a fluorene ring structure formed by bonding to each other.

20. A polycarbonate copolymer characterized in that,

having a siloxane structural unit represented by the formula (1) and a polycarbonate structural unit represented by the formula (3), wherein the proportion of a low-molecular weight compound having a weight-average molecular weight of 1000 or less, as calculated from the GPC area ratio, is 30% by weight or less,

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000,

y is any one of structural formulas shown in a formula (4),

c and d each independently represent 0 or an integer of 1 to 5000.

21. The polycarbonate copolymer of any of claims 17-20, wherein the siloxane structural units in the polycarbonate copolymer are present in a molar amount of 1 to 1000, and the polycarbonate structural units are present in a molar amount of 1 to 1000.

22. The polycarbonate copolymer of any of claims 17-21, wherein the molar ratio of siloxane structural units to polycarbonate structural units is from 0.01: 99.99 to 99.99: 0.01.

23. The polycarbonate copolymer of claim 22,

the molar ratio of the siloxane structural unit to the polycarbonate structural unit is 30.00: 70.00-99.9: 0.01.

24. The polycarbonate copolymer according to any one of claims 17 to 23, wherein the Q value is 8 x10 as measured at 280 ℃ and 160kgf^－2cm³s^－1The above.

25. A polycarbonate copolymer characterized in that,

having a siloxane structural unit represented by any one of formulas (1-1) to (1-4) and a polycarbonate structural unit represented by any one of formulas (3-1) to (3-4), wherein the total content of the cyclic bodies represented by formulas (5-1) to (5-3) is 4.0% by weight or less,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁are respectively provided withIndependently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000,

Z₃and Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Respectively independent earth surfaceAny one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

c and d each independently represent 0 or an integer of 1 to 5000,

in the formulae (5-1) to (5-3), m and n each represent the content of (-OSi (R) in each ring-shaped body₁R₂) The total number of structural units in the O-) site and the total number of structural units including the (-OC (═ O) O-) site,

in the formula (5-1), m represents an integer of 2 to 10,

in the formula (5-2), n represents an integer of 2 to 10,

in the formula (5-3), the sum of the values of m is 1 to 10, the sum of the values of n is 1 to 10, and the formula (5-3) contains (-OSi (R)₁R₂) The arrangement of the structural unit containing the O-) site and the structural unit containing the (-OC (═ O) O-) site is arbitrary,

in the formulae (5-1) to (5-3), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

R³～R¹⁰and R¹³～R²⁰Are respectively independentThe group is hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000.

26. The polycarbonate copolymer of any of claims 17-25,

the total content of the annular bodies of the formulae (6-1) to (6-2) is 2.0% by weight or less,

in the formulae (6-1) and (6-2),

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

R³～R¹⁰and R³⁰～R³³Each independently represents hydrogen, halogen, alkoxyA group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

n represents an integer of 2 to 10,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000.

27. The polycarbonate copolymer according to any one of claims 17 to 26, wherein the thermal decomposition temperature reduced by 1% by mass is 415 ℃ or lower.

28. A composition characterized in that it comprises, in a first aspect,

comprising the polycarbonate copolymer as defined in any one of claims 17 to 27 and a polycarbonate resin.

29. The composition of claim 28,

the total Si content in the composition is 0.1-20 mass%.

30. The composition according to one of claims 28 and 29,

the Q value of the composition is measured at 280 ℃ and 160kgf₁A Q value Q measured for measuring only the polycarbonate resin contained in the composition under the same conditions₂More than 120%.

31. A molded article obtained by molding the polycarbonate copolymer according to any one of claims 17 to 27.

32. An optical lens comprising the polycarbonate copolymer of any of claims 17-27.

33. An optical lens obtained by molding the composition according to any one of claims 28 to 30.

34. A process for producing a polysiloxane compound, which comprises the steps of,

comprising a polymerization step of polymerizing an oxysilane compound with a diol compound containing an aromatic diol compound or an alicyclic diol compound,

the oxysilane compound includes at least any one of a diaryloxysilane compound and a dialkoxysilane, wherein the diaryloxysilane compound is any one of a dialkyldiaryloxysilane, a diaryldiaryldiaryldiarylaryloxysilane, and a monoalkylmonoaryldiarylaryloxysilane, and the dialkoxysilane is any one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane,

in the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure while removing the formed aryl alcohol and/or alkyl alcohol by using a transesterification catalyst in a molar ratio of 0.01 to 16000. mu. mol/mol relative to the amount of the diol compound,

a poly (arylene/alkylene) siloxane compound having a weight average molecular weight of 10000 to 300000, which contains a structural unit represented by any one of the following formulas (1-1 ') to (1-4'),

in the formulae (1-1 ') to (1-4'), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

m₁～m₄each of which represents the total number of structural units in each formula and is a natural number of 10 to 1000,

x is a single bond or any of the structural formulae represented by the following formula (2),

in the formula (2), R¹¹And R¹²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R¹¹And R¹²Are bonded to each other to formThe carbon ring or the heterocycle having 1 to 20 carbon atoms which may have a substituent,

a and b each independently represent 0 or an integer of 1 to 5000.

35. The method for producing a polysiloxane compound according to claim 34,

Z₁and Z₂Each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 2 inclusive,

K₁each independently represents an integer of 0 to 2.

36. The method for producing a polysiloxane compound according to claim 34 or 35,

37. A process for producing a polysiloxane compound, which comprises the steps of,

comprising a polymerization step of polymerizing a diaryloxysilane compound containing at least one of a dialkyldiaryloxysilane, a diaryldiaryldiaryldiaryldiaryloxysilane, and a monoalkylmonoaryldiaryldiaryldiaryloxysilane with an aromatic diol compound,

in the polymerization step, the diaryloxysilane compound and the aromatic diol compound are polymerized in a molten state under reduced pressure while removing the aryl alcohol by using a transesterification catalyst in a molar ratio of 0.01 to 16000. mu. mol/mol relative to the amount of the aromatic diol compound,

a polyarylene siloxane compound having a weight average molecular weight of 10000 to 300000 and containing a structural unit represented by the following formula (1) is produced,

m represents a natural number of 10 to 1000,

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000.

38. The method for producing a polysiloxane compound according to any one of claims 34 to 37,

the reaction temperature in the polymerization step is in the range of 150 ℃ to 300 ℃.

39. The method for producing a polysiloxane compound according to any one of claims 34 to 38,

in the polymerization step, the reaction pressure is 101300Pa or less.

40. The method for producing a polysiloxane compound according to any one of claims 34 to 39, which comprises,

the polymerization step further comprises a pressure reduction step of gradually reducing the reaction pressure to 400Pa or less.

41. The method for producing a polysiloxane compound according to any one of claims 34 to 40,

in the polymerization step, the amount of the transesterification catalyst is 0.1 to 100. mu. mol/mol in terms of a molar ratio relative to the amount of the aromatic diol compound.

42. The method for producing a polysiloxane compound according to any one of claims 34 to 41,

the transesterification catalyst comprises an alkali metal compound and/or an alkaline earth metal compound.

43. The method for producing a polysiloxane compound according to claim 41, wherein the alkali metal compound and/or alkaline earth metal compound comprises 1 or more of carbonate, hydroxide, oxide and alkoxide.

44. The method for producing a polysiloxane compound according to claim 42, wherein the alkali metal compound and/or alkaline earth metal compound is a carbonate.

45. The method for producing a polysiloxane compound according to any one of claims 34 to 44,

no solvent is used in the polymerization step.

46. The method for producing a polysiloxane compound according to any one of claims 34 to 45,

the molar ratio of the diaryloxysilane compound to the aromatic diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

47. The method for producing a polysiloxane compound according to any one of claims 34 to 46,

in the polymerization step, the oxysilane compound or the diaryloxysilane compound and the diol compound or the aromatic diol compound are polymerized at a reaction temperature of more than 200 ℃ and/or under reduced pressure.

48. A polysiloxane compound, which is characterized in that,

comprising a structural unit represented by any one of formulas (1-1) to (1-4),

the weight average molecular weight of the polysiloxane compound is 5000-300000, and the total content of the cyclic bodies shown in the formula (5-4) is less than 4.0 wt%,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000,

in the formula (5-4), the arrangement of the structural unit represented by the formula (5-4) and other structural units is arbitrary, the total value of m is 2 to 10,

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

m represents an integer of 2 to 10,

x is a single bond or a structural formula represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000.

49. The polysiloxane compound of claim 48,

the total content of the annular bodies of the formulae (6-1) to (6-2) is 4.0% by weight or less,

in the formulae (6-1) and (6-2),

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

n represents an integer of 2 to 10,

x is a single bond or a structural formula represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000.

50. The silicone compound of claim 48 or 49,

the thermal decomposition temperature reduced by 1% by mass is 415 ℃ or lower.

51. A composition characterized in that it comprises, in a first aspect,

comprising the polysiloxane compound produced by the production method according to any one of claims 34 to 46 or the polysiloxane compound according to any one of claims 48 to 50, and a polycarbonate resin.

52. The composition of claim 51,

the total Si content in the composition is 0.1-20 mass%.

53. The composition according to one of claims 51 and 52,

54. A molded article obtained by molding the polysiloxane compound obtained by the production method according to any one of claims 34 to 46 or the polysiloxane compound according to any one of claims 48 to 50.

55. An optical lens comprising the polysiloxane compound produced by the production method described in any one of claims 34 to 46 or the polysiloxane compound described in any one of claims 48 to 50.

Technical Field

The present invention relates to a method for producing a polycarbonate copolymer and a polysiloxane compound, particularly a method for producing a polycarbonate copolymer having a siloxane structural unit, a polycarbonate copolymer, and the like.

Background

Thermoplastic polycarbonate resins have excellent impact resistance and mechanical properties, can be formed into various molded articles by a simple and high-productivity processing method such as injection molding, and are used in a wide range of industrial fields such as electric and electronic fields, OA equipment, heavy motors, precision instruments, and automobile fields.

The conventional polycarbonate resin has a disadvantage of poor flowability due to high melt viscosity, and it is difficult to realize injection molding of precision parts or thin articles. Therefore, in the prior art, it is necessary to increase the temperature during molding, which causes problems such as an increase in cost due to an increase in molding cycle at high temperature, and deterioration of polycarbonate resin during molding. Therefore, attempts have been made to improve the flowability of polycarbonate resins (patent documents 1 and 2), but it is not always possible to achieve sufficiently high flowability without impairing the inherent properties (impact resistance and the like) of polycarbonate resins.

In addition to polycarbonate resins, polymers of aromatic polysiloxanes, also called so-called polyarylene siloxanes, are known as materials for molded articles obtained by molding methods such as injection molding (for example, patent document 3). In recent years, importance of polysiloxane compounds such as polyarylene siloxane has been increased, and polyarylene siloxane is used as a release layer in photolithography, a photoresist material, a plasticizer for polycarbonate, a component of a powder surface coating system, and the like.

As a method for producing a polysiloxane compound such as polyarylene siloxane, a method of reacting dimethyldichlorosilane and bisphenol a in a solvent to generate hydrochloric acid (non-patent document 1), a method of reacting in a solvent to which acetic acid is added (patent document 4), and the like are known.

However, polycarbonate resins, polysiloxane compounds, and the like which are particularly suitable for specific applications such as optical applications have not been realized.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-148047

Patent document 2: japanese laid-open patent publication No. 62-297319

Patent document 3: japanese Kohyo publication Hei 08-502537

Patent document 4: japanese laid-open patent publication No. 2015-512999

Non-patent document

Non-patent document 1: journal of Polymer Science, Vol.18,3119-3127(1980)

Disclosure of Invention

Technical problem to be solved by the invention

The present invention provides a polycarbonate copolymer having siloxane structural units, which has excellent impact resistance and high fluidity when melted, a method for efficiently producing the polycarbonate copolymer, and the like.

The present invention also provides a safe and efficient method for producing a polycarbonate copolymer having a siloxane structural unit and a polysiloxane compound. For example, a method is provided by which a polysiloxane compound such as a polycarbonate copolymer or polyarylene siloxane can be efficiently produced without generation of corrosive substances such as hydrochloric acid or acetic acid and without using a solvent, while reducing environmental load.

The present invention further provides a polycarbonate resin, a polysiloxane compound, and the like which are particularly suitable for specific applications such as optical applications.

Means for solving the problems

The present invention provides a polycarbonate copolymer comprising siloxane structural units, having excellent impact resistance and high fluidity, a method for producing the polycarbonate copolymer, and the like.

Also disclosed is a method for efficiently producing a polycarbonate copolymer or a polysiloxane compound, which can be carried out without generating a by-product such as an acid which is highly environmentally responsible and without using a solvent, particularly a solvent which is considered to be safe.

[1] A method for producing a polycarbonate copolymer, comprising a polymerization step of polymerizing a silane compound, a carbonate compound and a diol compound containing an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst,

the silane compound is selected from a diaryloxysilane compound, a dialkoxysilane compound, and a silicon compound, the diaryloxysilane compound includes at least one of a dialkyldiaryloxysilane, a diaryldiaryldiaryldiaryldiaryldiarylaryloxysilane, and a monoalkyl monoaryldiarylaryloxysilane, the dialkoxysilane contains at least one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkyl monoaryldialkoxysilane, the silicon compound includes at least one of a cyclic siloxane compound and a linear siloxane compound,

(in formulae (1-1) to (1-4), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

(in the formula (2), R¹¹And R¹²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R¹¹And R¹²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

a and b each independently represent 0 or an integer of 1 to 5000. )

(in formulae (3-1) to (3-4), R¹³～R²⁰And R⁴⁰～R⁵¹Each independently represents hydrogen, halogen, or alkaneAn oxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent,

Z₃and Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

(in the formula, R²¹And R²²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R²¹And R²²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

c and d each independently represent 0 or an integer of 1 to 5000. )

[2]As described above [1]The method for producing a polycarbonate copolymer, wherein Z₁～Z₄Each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁and J₂Each independently represents an integer of 0 to 2 inclusive,

K₁and K₂Each independently represents an integer of 0 to 2.

[3]As described above [1]Or [ 2]]The method for producing a polycarbonate copolymer, wherein X has R¹¹And R¹²Siloxane structural units having a fluorene ring structure formed by bonding the siloxane structural units to each other, and/or Y has R²¹And R²²And a polycarbonate structural unit having a fluorene ring structure formed by bonding to each other.

[4] A method for producing a polycarbonate copolymer, comprising a polymerization step of polymerizing a silane compound, a carbonate compound and a diol compound containing an aromatic diol compound or an alicyclic diol compound in the presence of a transesterification catalyst,

the silane compound is selected from a diaryloxysilane compound, a dialkoxysilane compound, and a silicon compound, the diaryloxysilane compound includes at least one of a dialkyldiaryloxysilane, a diaryldiaryldiaryldiaryldiaryldiarylaryloxysilane, and a monoalkyl monoaryldiarylaryloxysilane, the dialkoxysilane compound includes at least one of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkyl monoaryldialkoxysilane, the silicon compound includes at least one of a cyclic siloxane compound and a linear siloxane compound,

(in the formula (1), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

(in the formula, R¹³～R²⁰Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

y is any one of structural formulas shown in a formula (4),

c and d each independently represent 0 or an integer of 1 to 5000. )

[5] The method for producing a polycarbonate copolymer according to any one of the above [1] to [4], wherein the transesterification catalyst contains an alkali metal compound and/or an alkaline earth metal compound.

[6] The method for producing a polycarbonate copolymer according to [5], wherein the alkali metal compound and/or the alkaline earth metal compound contains a carbonate.

[7] The method for producing a polycarbonate copolymer according to any one of the above [1] to [6], wherein the polycarbonate copolymer has a weight average molecular weight of 10000 to 300000.

[8]As described above [1]～[7]The method for producing a polycarbonate copolymer according to any one of the above methods, wherein in the polymerization step, the molar ratio of the transesterification catalyst to the amount of the diol compound is 1.0X 10^－7～1.0×10^－2。

[9] The method for producing a polycarbonate copolymer according to any one of the above [1] to [8], wherein the reaction temperature in the polymerization step is in the range of 150 ℃ to 300 ℃.

[10] The method for producing a polycarbonate copolymer according to any one of the above [1] to [9], further comprising a pressure reduction step of gradually reducing the reaction pressure to 400Pa or less in the polymerization step.

[11] The method for producing a polycarbonate copolymer according to any one of the above [1] to [10], wherein in the polymerization step, the carbonate compound and the diol compound are polymerized under a pressure of 400Pa or less.

[12] The method for producing a polycarbonate copolymer according to any one of the above [1] to [11], wherein a solvent is not used in the polymerization step.

[13] The method for producing a polycarbonate copolymer according to any one of the above [1] to [12], wherein the ratio of the total mole number of the carbonate compound and the diaryloxysilane compound used in the polymerization step to the mole number of the diol compound is 0.9 or more and 1.2 or less.

[14] The method for producing a polycarbonate copolymer according to any one of the above [1] to [13], wherein the polycarbonate copolymer has 1 to 1000 mol of the siloxane structural unit and 1 to 1000 mol of the polycarbonate structural unit.

[15] The method for producing a polycarbonate copolymer according to any one of the above [1] to [14], wherein the molar ratio of the siloxane structural unit to the polycarbonate structural unit is 0.01: 99.99 to 99.99: 0.01.

[16]As described above [1]～[15]The method for producing a polycarbonate copolymer, wherein the polycarbonate copolymer has a Q value of 8(× 10) measured at 280 ℃ and 160kgf^－2cm³s^－1) The above.

[17] A polycarbonate copolymer which comprises a siloxane structural unit represented by any one of the formulae (1-1) to (1-4) and a polycarbonate structural unit represented by any one of the formulae (3-1) to (3-4), and in which the weight-average molecular weight of a low-molecular-weight compound having a weight-average molecular weight of 1000 or less is 30% by weight or less.

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

(in formulae (3-1) to (3-4), R¹³～R²⁰And R⁴⁰～R⁵¹Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

Z₃and Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

c and d each independently represent 0 or an integer of 1 to 5000. )

[18]As described above [17]The polycarbonate copolymer, wherein Z₁～Z₄Each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁and J₂Each independently represents an integer of 0 to 2 inclusive,

K₁and K₂Each independently represents 0 to 2Is an integer of (1).

[19]As described above [17]Or [18 ]]The polycarbonate copolymer, wherein X has the formula R¹¹And R¹²Siloxane structural units having a fluorene ring structure formed by bonding the siloxane structural units to each other, and/or Y has R²¹And R²²And a polycarbonate structural unit having a fluorene ring structure formed by bonding to each other.

[20] A polycarbonate copolymer having a siloxane structural unit represented by formula (1) and a polycarbonate structural unit represented by formula (3), wherein the proportion of a low molecular weight compound having a weight average molecular weight of 1000 or less, as calculated from a GPC area ratio, is 30% by weight or less.

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

y is any one of structural formulas shown in a formula (4),

c and d each independently represent 0 or an integer of 1 to 5000. )

[21] The polycarbonate copolymer according to any one of the above [17] to [20], wherein the number of moles of the siloxane structural unit in the polycarbonate copolymer is 1 to 1000, and the number of moles of the polycarbonate structural unit in the polycarbonate copolymer is 1 to 1000.

[22] The polycarbonate copolymer according to any one of [17] to [21], wherein the molar ratio of the siloxane structural unit to the polycarbonate structural unit is 0.01: 99.99 to 99.99: 0.01.

[23] The polycarbonate copolymer according to [22], wherein the molar ratio of the siloxane structural unit to the polycarbonate structural unit is 30.00: 70.00 to 99.9: 0.01.

[24]As described above [17]～[23]The polycarbonate copolymer as described in any one of the above, wherein the Q value measured at 280 ℃ and 160kgf is 8(× 10)^－2cm³s^－1) The above.

[25] A polycarbonate copolymer which comprises a siloxane structural unit represented by any one of the formulae (1-1) to (1-4) and a polycarbonate structural unit represented by any one of the formulae (3-1) to (3-4), wherein the total content of cyclic bodies represented by the formulae (5-1) to (5-3) is 4.0% by weight or less.

(formulae (1-1) to (1-4), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

Z₃and Z₄Each independently may have a fetchAn alkylene group having 1 to 5 carbon atoms as a substituent,

J₂each independently represents an integer of 0 to 5 inclusive,

K₂each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

y is a single bond or any of the structural formulae represented by the formula (4),

c and d each independently represent 0 or an integer of 1 to 5000. )

(in formulae (5-1) to (5-3), m and n each represent the content of (-OSi (R) in each ring-shaped body₁R₂) The total number of structural units in the O-) site and the total number of structural units including the (-OC (═ O) O-) site,

in the formula (5-1), m represents an integer of 2 to 10,

in the formula (5-2), n represents an integer of 2 to 10,

R³～R¹⁰and R¹³～R²⁰Each independently represents hydrogen, halogen, alkoxy, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkenyl having 2 to 20 carbon atoms or optionally substituted aryl having 6 to 30 carbon atoms,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. ))

[26] The polycarbonate copolymer according to any one of the above [17] to [25], wherein the total content of the cyclic bodies of the formulas (6-1) to (6-2) is 2.0% by weight or less.

(in the formulae (6-1) and (6-2),

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

n represents an integer of 2 to 10,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

[27] The polycarbonate copolymer according to any one of the above [17] to [26], wherein the thermal decomposition temperature decreased by 1% by mass is 415 ℃ or lower.

[28] A composition comprising the polycarbonate copolymer according to any one of the above [17] to [27] and a polycarbonate resin.

[29] The composition according to [28], wherein the total Si content in the composition is 0.1 to 20% by mass.

[30]As described above [28]And [29]]The composition according to any one of the preceding claims, wherein the composition has a Q value Q measured at 280 ℃ and 160kgf₁A Q value Q measured by measuring only the polycarbonate resin contained in the composition under the same conditions₂More than 120%.

[31] A molded article obtained by molding the polycarbonate copolymer according to any one of the above [17] to [27 ].

[32] An optical lens comprising the polycarbonate copolymer according to any one of [17] to [27 ].

[33] An optical lens obtained by molding the composition according to any one of [28] to [30 ].

[34] A process for producing a polysiloxane compound, which comprises the steps of,

comprising a polymerization step of polymerizing an oxysilane compound with a diol compound containing an aromatic diol compound or an alicyclic diol compound,

the oxysilane compound includes at least one of a diaryloxysilane compound and a dialkoxysilane, the diaryloxysilane compound is any of a dialkyldiarylaryloxysilane, a diaryldiaryldiaryldiarylaryloxysilane, and a monoalkylmonoaryldiarylaryloxysilane, the dialkoxysilane compound is any of a dialkyldialkoxysilane, a diaryldialkoxysilane, and a monoalkylmonoaryldialkoxysilane,

in the polymerization step, the oxysilane compound and the diol compound are polymerized in a molten state under reduced pressure while removing the formed aryl alcohol and/or alkyl alcohol by using an ester exchange catalyst in a molar ratio of 0.01 to 16000. mu. mol/mol relative to the amount of the diol compound,

(in the formulae (1-1 ') to (1-4'), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

m₁～m₄each of which represents the total number of structural units in each formula and is a natural number of 10 to 1000,

x is a single bond or any of the structural formulae represented by the following formula (2),

(in the formula, R¹¹And R¹²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R¹¹And R¹²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

a and b each independently represent 0 or an integer of 1 to 5000. )

[35]As described above [34]The process for producing the polysiloxane compound, wherein Z₁And Z₂Each independently an alkylene group having 1 to 3 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 2 inclusive,

K₁each independently represents an integer of 0 to 2.

[36]As described above [34]Or [35]The process for producing a polysiloxane compound, wherein X represents R¹¹And R¹²Siloxane structural units having a fluorene ring structure formed by bonding the siloxane structural units to each other, and/or Y has R²¹And R²²And a polycarbonate structural unit having a fluorene ring structure formed by bonding to each other.

[37] A method for producing a polysiloxane compound, comprising a polymerization step of polymerizing a diaryloxysilane compound containing at least one of dialkyldiarylaryloxysilane, diaryldiaryldiaryldiarylaryloxysilane, and monoalkylmonoaryldiarylaryloxysilane, with an aromatic diol compound,

a polyarylene siloxane compound having a weight average molecular weight of 10000 to 300000 and containing a structural unit represented by the following formula (1) is produced.

(in the formula, R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

m represents a natural number of 10 to 1000,

x is any one of structural formulas shown in the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

[38] The method for producing a polysiloxane compound according to any one of [34] to [37], wherein the reaction temperature in the polymerization step is in the range of 150 ℃ to 300 ℃.

[39] The method for producing a polysiloxane compound according to any one of [34] to [38], wherein the reaction pressure in the polymerization step is 101300Pa or less.

[40] The method for producing a polysiloxane compound according to any one of the above [34] to [39], wherein the polymerization step further comprises a pressure reduction step of gradually reducing the reaction pressure to 400Pa or less.

[41] The method for producing a polysiloxane compound according to any one of [34] to [40], wherein, in the polymerization step, the ester exchange catalyst is present in a molar ratio of 0.1 to 100. mu. mol/mol relative to the amount of the aromatic diol compound.

[42] The method for producing a polysiloxane compound according to any one of [34] to [41], wherein the transesterification catalyst comprises an alkali metal compound and/or an alkaline earth metal compound.

[43] The method for producing a polysiloxane compound according to [41], wherein the alkali metal compound and/or alkaline earth metal compound comprises 1 or more of any of a carbonate, a hydroxide, an oxide, and an alkoxide.

[44] The method for producing a polysiloxane compound according to [42], wherein the alkali metal compound and/or alkaline earth metal compound is a carbonate.

[45] The method for producing a polysiloxane compound according to any one of [34] to [44], wherein a solvent is not used in the polymerization step.

[46] The method for producing a polysiloxane compound according to any one of [34] to [45], wherein the molar ratio of the diaryloxysilane compound to the aromatic diol compound used in the polymerization step is 0.9 or more and 1.2 or less.

[47] The method for producing a polysiloxane compound according to any one of the above [34] to [46], wherein in the polymerization step, the oxysilane compound or the diaryloxysilane compound and the diol compound or the aromatic diol compound are polymerized at a reaction temperature of higher than 200 ℃ and/or under reduced pressure.

[48] A polysiloxane compound which comprises structural units shown in any one of formulas (1-1) to (1-4), wherein the weight average molecular weight of the polysiloxane compound is 5000-300000, and the total content of the annular bodies shown in the formula (5-4) is less than 4.0 wt%.

Z₁and Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

J₁each independently represents an integer of 0 to 5 inclusive,

K₁each independently represents an integer of 0 to 5 inclusive,

A₁and A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3 inclusive,

x is a single bond or any of the structural formulae represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

(in the formula (5-4), the arrangement of the structural unit represented by the formula (5-4) and other structural units is arbitrary, the total value of m is 2 to 10,

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

m represents an integer of 2 to 10,

x is a single bond or a structural formula represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. ))

[49] The polysiloxane compound according to [48], wherein the total content of the cyclic bodies of formulae (6-1) to (6-2) is 4.0% by weight or less.

(in the formulae (6-1) and (6-2),

R¹and R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent,

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent,

i and ii each independently represent an integer of 0 to 5,

n represents an integer of 2 to 10,

x is a single bond or a structural formula represented by the following formula (2),

a and b each independently represent 0 or an integer of 1 to 5000. )

[50] The polysiloxane compound according to [48] or [49], wherein the thermal decomposition temperature reduced by 1% by mass is 415 ℃ or lower.

[51] A composition comprising the polysiloxane compound produced by the production method according to any one of the above [34] to [46] or the polysiloxane compound according to any one of the above [48] to [50], and a polycarbonate resin.

[52] The composition according to [51], wherein the total Si content in the composition is 0.1 to 20% by mass.

[53]As described above [51]]And [52]]The composition according to any one of the preceding claims, wherein the composition has a Q value Q measured at 280 ℃ and 160kgf₁A Q value Q measured for measuring only the polycarbonate resin contained in the composition under the same conditions₂More than 120%.

[54] A molded article obtained by molding the polysiloxane compound obtained by the production method according to any one of the above [34] to [46] or the polysiloxane compound according to any one of the above [48] to [50 ].

[55] An optical lens comprising the polysiloxane compound produced by the production method according to any one of the above [34] to [46] or the polysiloxane compound according to any one of the above [48] to [50 ].

Effects of the invention

According to the method for producing a polycarbonate copolymer of the present invention, a polycarbonate copolymer having siloxane structural units with high fluidity in the melt can be produced. Further, according to the present invention, a polycarbonate copolymer having such excellent characteristics, a composition containing the polycarbonate copolymer, and a molded article obtained by molding the polycarbonate copolymer can be realized.

Further, according to the method for producing a polycarbonate copolymer and the method for producing a polyarylene compound of the present invention, a desired compound such as polyarylene siloxane can be efficiently produced without producing a by-product such as an acid which is highly environmentally friendly and without requiring a solvent. The present invention also enables to obtain a polyarylene compound such as polyarylene siloxane having excellent properties.

Detailed Description

[ polycarbonate copolymer ]

The method for producing a polycarbonate copolymer of the present invention includes a polymerization step of polymerizing at least 1 or more kinds of silane compounds selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane, and a predetermined silicon compound (siloxane compound), a carbonate compound, and an aromatic diol compound in the presence of a transesterification catalyst, which will be described in detail later.

The above polymerization reaction is summarized as follows. For example, a diaryloxysilane compound (Si (CH) having 2 methyl groups and a phenoxy group as an example of the silane-based compound₃)₂(OPh)₂) When diphenyl carbonate (PhO-CO-OPh) as an example of the carbonate compound and bisphenol A as an example of the aromatic diol compound were reacted, the following polycarbonate copolymer was obtained.

That is, a polycarbonate copolymer having, for example, a siloxane structural unit formed by the reaction of the following formula (A) and, for example, a polycarbonate structural unit formed by the reaction of the following formula (B) is obtained.

In this polymerization reaction, an alcohol derived from a carbonate compound is produced as a by-product as described below, and for example, when diaryl carbonate is used as the carbonate compound, an aryl alcohol such as phenol (PhOH) is produced. Therefore, in the polymerization step, the polymerization reaction is carried out while removing an alcohol as a by-product, for example, an aryl alcohol such as phenol under reduced pressure in a state where the mixture of the above components is melted.

The method for producing the polycarbonate copolymer of the present invention will be described in detail below.

< 1. method for producing polycarbonate copolymer

[ (I) silane-based Compound ]

The silane compound used in the polymerization step is used to form a siloxane structural unit in the polycarbonate copolymer, for example, as represented by the formula (a). The silane compound is of a type which can form a polymer containing-OSi (R) (described in detail later) in the main chain of the polycarbonate copolymer¹R²) The siloxane structural unit of the O-site is not particularly limited, and may be selected from a predetermined diaryloxysilane compound, a predetermined dialkoxysilane, and a predetermined silicon compound (siloxane compound).

That is, in the polymerization step, a silane compound containing at least any one of diaryloxysilane compounds, at least any one of dialkoxysilanes, and at least any one of silicon compounds, which will be described in detail later, is used. The silane-based compound may be a mixture of a plurality of diaryloxysilane compounds, a plurality of dialkoxysilanes, a plurality of silicon compounds, a mixture of diaryloxysilane compounds and silicon compounds, a mixture of dialkoxysilanes and silicon compounds, or a mixture of diaryloxysilane compounds and dialkoxysilanes. The diaryloxysilane compound is explained below.

(A-1) Diaryloxysilane Compound

As the diaryloxysilane compound, there can be mentioned dialkyldiaryldiaryldiaryldiaryldiaryldiaryloxysilane, and monoalkylmonoaryldiaryldiaryldiaryldiaryldiaryldiaryldiaryldiaryldiaryloxysilane. That is, in the polymerization step, any one or more of them may be used as the silane-based compound.

In the general formula Si (R)^aR^b)(OAr)₂When represents a diaryloxysilane compound, R^aAnd R^bEach independently selected from alkyl and aryl. Preferably R^aAnd R^bIndependently represents an alkyl group having 1 to 20 carbon atoms in total and an aryl group having 6 to 30 carbon atoms in total, which may have a substituent. At R^aAnd R^bIn the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

In addition, in R^aAnd R^bIn the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

Examples of the substituent include a hydroxyl group, a halogen group, an amino group, a vinyl group, a carboxyl group, a cyano group, (meth) acryloyloxy group, a glycidoxy group, a mercapto group and the like.

As R in formula (1)^aAnd R^bAs preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

Further, it is understood from the above formula (A) that the aryloxy group (OAr group) of the silane compound is not introduced into the polymer chain of the polycarbonate copolymer, but a by-product (ArOH) such as phenol is produced. Therefore, the kind of the aryloxy group is not particularly limited. However, in order to remove by-products in the polymerization step from the reaction system as easily as possible, the aryloxy group is preferably a group having low polarity and molecular weight, such as phenoxy group.

Specific examples of the dialkyldiaryloxysilane include dimethyldiphenoxysilane, methylethyldiphenoxysilane, diethyldiphenoxysilane, and the like. Specific examples of diaryldiaryldiaryldiaryldiaryldiarylaryloxysilanes include diphenyldiphenoxysilane. Specific examples of the monoalkylmonoaryldiaryldiaryloxysilane include methylphenylphenoxysilane and the like.

(A-2) dialkoxysilanes

Examples of dialkoxysilanes include dialkyldialkoxysilanes, diaryldialkoxysilanes, and monoalkylmonoaryldialkoxysilanes. That is, in the polymerization step, any one or more of them may be used as the silane-based compound.

In the general formula Si (R)^aR^b)(OR^c)₂When represents a dialkoxysilane compound, R^aAnd R^bEach independently with R described in (A-1) diaryloxysilane compound^aAnd R^bSame, selected from alkyl and aryl.

Further, from the above formula (A), it is clear that the alkoxy group (OR) of the silane compound^cRadical) does not introduce into the polymer chain of the polycarbonate copolymer, but generates a by-product (MeOH), for example, methanol. Therefore, the kind of the alkoxy group is not particularly limited. However, in order to remove the by-product in the polymerization step from the reaction system as easily as possible, an alkoxy group (OR)^cRadical) is, for example, methoxy.

Specific examples of the dialkyldialkoxysilanes include dimethyldimethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, and the like. Specific examples of the diaryldialkoxysilane include diphenyldimethoxysilane. Specific examples of the monoalkylmonoaryldialkoxysilane include methylphenyldimethoxysilane and the like.

(B) Silicon compound (siloxane compound)

The silicon compound is explained below. The silicon compound includes a predetermined cyclic siloxane compound and a predetermined linear siloxane compound. That is, in the polymerization step, any of them may be used as the silane-based compound.

(B-1) Cyclic siloxane Compound

Examples of the siloxane compound used in the polymerization step include a cyclic siloxane compound represented by the following formula (5).

In the formula (5), R^cAnd R^dEach independently represents an alkyl group, an alkenyl group or an aryl group which may have a substituent. R in the formula (5)^cAnd R^dPreferably, the alkyl groups are each independently an alkyl group having 1 to 20 carbon atoms in total or an aryl group having 6 to 30 carbon atoms in total, which may have a substituent.

At R^cAnd R^dIn the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

In addition, in R^cAnd R^dIn the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

As R in formula (5)^cAnd R^dAs preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

The cyclic siloxane compound has a siloxane structure, and the siloxane structure includes the above-mentioned R^cRadical and R^dOf the group-OSi (R)^cR^d) An O-structure. In the polymerization step, the-OSi (R) of the cyclic siloxane compound is reacted with^cR^d) The O-site is introduced into a polycarbonate copolymer described later in detail.

In the formula (5), n represents an integer of 3 to 30 inclusive. The value of n in formula (5) is preferably 3 to 15, more preferably 3 to 10, even more preferably 3 to 8, and particularly preferably 3 to 5.

The molecular weight of the cyclic siloxane compound represented by formula (5) is preferably 2000 or less, more preferably 1600 or less, still more preferably 1200 or less, and particularly preferably 1000 or less. The molecular weight of the cyclic siloxane compound represented by formula (5) is, for example, 100 or more, preferably 150 or more, and more preferably 200 or more.

(B-2) Linear siloxane Compound

The siloxane compound used in the polymerization step may be a linear siloxane compound represented by the following formula (6).

In the formula (6), R^eAnd R^fEach independently represents an alkyl group or an aryl group which may have a substituent. R in the formula (6)^eAnd R^fThe alkyl groups are preferably alkyl groups having 1 to 20 carbon atoms in total or aryl groups having 6 to 30 carbon atoms in total, which may have a substituent.

At R^eAnd R^fIn the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 or 2.

In addition, in R^eAnd R^fIn the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

As R in formula (6)^eAnd R^fAs preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

The linear siloxane compound also has a siloxane structure, and examples of the siloxane structure include those having the above-mentioned R^eRadical and R^fOf the group-OSi (R)^eR^f) An O-structure. In the polymerization step, linear siloxane is alkylatedCompound of formula (I) < CHEM > (R)^eR^f) The O-site is introduced into a polycarbonate copolymer described later in detail.

In formula (6), m represents an integer of 2 to 10000. The value of m in formula (6) is preferably 10 to 7000, more preferably 100 to 2000, and still more preferably 200 to 500.

In the formula (6), X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 total carbon atoms which may have a substituent, a hydrocarbon group having 1 to 10 total carbon atoms which may have a substituent and may have an oxygen atom or a nitrogen atom, or an amino group which may have a substituent. X is preferably any one of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 total carbon atoms which may have a substituent, and an alkyl group having 1 to 10 total carbon atoms which may have a substituent and may have an oxygen atom or a nitrogen atom, more preferably a hydroxyl group or an alkyl group having 1 to 10 total carbon atoms which may have a substituent, and still more preferably a hydroxyl group or an alkyl group having 1 to 5 total carbon atoms.

Examples of the substituent for X include a hydroxyl group, a halogen group, an amino group, a vinyl group, a carboxyl group, a cyano group, (meth) acryloyloxy group, glycidoxy group, a mercapto group and the like.

The molecular weight of the linear siloxane compound represented by formula (6) is preferably 60000 or less, more preferably 56000 or less, still more preferably 50000 or less, and particularly preferably 45000 or less. The molecular weight of the linear siloxane compound represented by formula (6) is, for example, 1000 or more, preferably 5000 or more, and more preferably 10000 or more.

Only a single siloxane compound of the cyclic siloxane compound of the formula (5) and the linear siloxane compound of the formula (6) may be used, and 2 or more siloxane compounds may be used as a mixture. Further, the siloxane compound of the formula (5) or (6) may be used in combination with the diaryloxysilane compound (A).

The silane-based compound can be synthesized by a known method, or a commercially available product can be used.

[ (II) carbonate Compound ]

The carbonate compound is used to introduce a carbonyl group (-CO-group) of a polycarbonate structural unit into the polycarbonate copolymer, as shown in the above formula (B) regarding the outline of the polymerization reaction. That is, 2-OR groups of the carbonate compound represented by the general formula RO-CO-OR (R is independently selected from aryl, alkyl and aralkyl groups), for example, 2 aryloxy groups (ArO-groups) in the case where the carbonate compound is a diaryl carbonate represented by the general formula ArO-CO-OAr, are not introduced into the polymer chain of the polycarbonate copolymer. these-OR groups form an alcohol derived from a carbonate compound as a by-product, for example, an aryl alcohol (ArOH) as a by-product, such as a carbonate compound having an aryloxy group (ArO-group) (a monoaryl carbonate OR a diaryl carbonate) to form phenol.

Therefore, the kind of the aryl group, the alkyl group and the aralkyl group of the carbonate compound is not particularly limited. However, in order to remove the by-product in the polymerization step from the reaction system as easily as possible, it is preferable that the group-OR of the above general formula is an aryloxy group (OR the group-R of the above general formula RO-CO-OR is an aryl group), and it is more preferable that the polarity and molecular weight of the carbonate compound are low, and the group-OR of the above general formula is, for example, a phenoxy group.

As described above, in the carbonate compound, it is preferable that one or both of the Ar groups be an aryl group having 10 or less carbon atoms in total, for example, a phenyl group, a benzyl group, or the like. That is, preferable specific examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, diphenylmethyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and monoaryl monoalkyl carbonate.

The above carbonate compound can be synthesized by a known method, and a commercially available product can be used.

[ (III-1) aromatic diol Compound ]

The aromatic diol compound used in the polymerization step is used to constitute the main chain of the polycarbonate copolymer, as shown in the above formulae (a) and (B) regarding the outline of the polymerization reaction.

Therefore, as the aromatic diol compound used in the polymerization step, monomers capable of serving as a material of the polycarbonate resin are preferable, and examples thereof include bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 1, 2-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2-bis (4-hydroxy-3-methylphenyl) propane, 1-bis (4-hydroxy-3-tert-butylphenyl) propane, and the like, 2, 2-bis (3, 5-dimethyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-phenylphenyl) propane, 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3-methoxyphenyl) propane, 4 '-dihydroxydiphenyl ether, 4' -dihydroxy-3, 3 '-dimethylphenyl ether, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane, 1-bis (4-hydroxyphenyl) cyclopentane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3-methoxyphenyl) propane, 4' -dihydroxydiphenyl ether, 4 '-dihydroxy-3, 3' -dimethylphenyl ether, 2-bis (4-hydroxy-bromophenyl) propane, 2-hydroxy-4-hydroxy-phenyl ether, 2-bis (4-hydroxy-4-hydroxy-hydroxyphenyl) propane, 2, 4-hydroxy-4-hydroxy-4-2, 4-hydroxy-phenyl ether, 2, 4-hydroxy-phenyl ether, 2, 4-hydroxy-4-phenyl ether, 2, 4-hydroxy-3-hydroxy-4-hydroxy-3, 2, 4-hydroxy-3, 2, or the like, 2, or the like, 4,4 ' -dihydroxyphenyl sulfide, 4 ' -dihydroxy-3, 3' -dimethyldiphenyl sulfide, 4 ' -dihydroxydiphenyl sulfoxide, 4 ' -dihydroxy-3, 3' -dimethyldiphenyl sulfoxide, 4 ' -dihydroxydiphenyl sulfone, 4 ' -dihydroxy-3, 3' -dimethyldiphenyl sulfone, 2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2-bis (3-bromo-4-hydroxyphenyl) propane, 1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4,4 ' -dihydroxybiphenyl, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 4 ' -sulfonyldiphenol, 2' -diphenyl-4, 4 ' -sulfonyldiphenol, 2' -dimethyl-4, 4 ' -sulfonyldiphenol, 1, 3-bis {2- (4-hydroxyphenyl) propyl } benzene, 1, 4-bis (4-hydroxyphenyl) cyclohexane, 1, 3-bis (4-hydroxyphenyl) cyclohexane, 4, 8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4 ' - (1, 3-adamantanediyl) diphenol, 1, 3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 9-bis (4- (2-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene, 2 '-bis (2-hydroxyethoxy) -1, 1' -Binaphthyl (BNE), 9-bis (6- (2-hydroxyethoxy) naphthalen-2-yl) fluorene (BNEF), 2,2 '-bis (2-hydroxyethoxy) -6, 6' -diphenyl-1, 1 '-binaphthyl, 2' -bis (2-hydroxyethoxy) -6,6 '-bis (phenanthren-9-yl) -1, 1' -binaphthyl, and the like.

Among these, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF), 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (BPPEF), and 9, 9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene (BPMEF) are preferable, and 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (BPEF) and 9, 9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene (BPPEF) are more preferable.

[ (III-2) alicyclic diol Compound ]

The alicyclic diol compound used in the polymerization step includes the following compounds.

Namely, isosorbide represented by the following formula (in the above formula (1-3), L₁And L₂Is 1, A₁And A₂Is an oxygen atom and J₁、K₁、J₂And K₂A compound of 0):

spirocyclic ethylene glycol (SPG) represented by the following formula:

decahydro-1, 4:5, 8-dimethylnaphthalene diol (D-NDM, a compound wherein R is hydrogen) represented by the following formula:

(R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably R represents hydrogen),

Cyclohexanedimethanol represented by the formula:

pentacyclopentadecane dimethanol (PCPMD) represented by the following formula:

tricyclodecanedimethanol (TCDDM) of the formula:

adamantane dimethanol such as 1, 3-adamantane dimethanol represented by the following formula:

and the like.

It is preferable to include structural units derived from these alicyclic diols in the main chain of the polycarbonate copolymer.

The polycarbonate copolymer has high fluidity and is suitable for forming a molded article, for example, a thin sheet, a film, or the like.

[ (IV) transesterification catalyst ]

The transesterification catalyst used in the polymerization step is preferably a catalyst containing a basic compound. Examples of the basic compound catalyst include catalysts containing an alkali metal compound, an alkaline earth metal compound, and the like. Examples of such compounds include organic acid salts such as alkali metal and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, and alkanols. Alternatively, as the basic compound catalyst, quaternary ammonium bases, salts thereof, amines, and the like can be used. In addition, these compounds may be used alone, or a plurality of them may be used in combination.

The transesterification catalyst more preferably contains an alkali metal carbonate or an alkali metal hydroxide among the above-mentioned basic compound catalysts. Specific examples of more preferable transesterification catalysts include catalysts containing cesium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, and the like.

The transesterification catalyst may be prepared by a known method, or a commercially available product may be used.

[ (V) polymerization procedure ]

In the polymerization step, at least the silane compound (I), the carbonate compound (II), and the aromatic diol compound (III) are polymerized in the presence of the transesterification catalyst (IV). In this polymerization reaction, a mixture of the above components is melted to be in a molten state, and an alcohol derived from a carbonate compound, for example, an aryl alcohol, is removed as a by-product under reduced pressure. By setting the reaction conditions in this manner, the polymerization reaction can be efficiently performed.

In the polymerization step, the polymerization reaction is preferably carried out under a pressure of 400Pa or less. I.e. the process is repeated. The pressure of the polymerization reaction is preferably in the range of 400Pa or less.

In the polymerization step, it is preferable to maintain the system in a non-reduced pressure normal pressure state or a state of not being reduced in pressure for a certain period of time, and then reduce the pressure in the system to further perform the polymerization reaction. For example, in the polymerization step, the reaction pressure is preferably gradually reduced to 400Pa or less from 27000Pa, 24000Pa, 20000Pa, 16000Pa, 8000Pa, 4000Pa, 2000Pa, 400Pa, or less from the first atmospheric pressure. Such a pressure reduction step of reducing the pressure in the reaction system stepwise to increase the reduced pressure from the middle is preferable because distillation of the raw material can be suppressed and the alcohol as a by-product can be efficiently removed.

The time of the polymerization step may be appropriately determined in consideration of conditions such as the type, pressure, and temperature of the desired polycarbonate copolymer, and for example, the total time consumed in the polymerization step is within 5 to 10 hours. More specifically, the reaction time before the pressure reduction in the reaction system is 0.5 to 3 hours, preferably 1 to 2 hours, and the reaction time after the pressure reduction is 1 to 5 hours, preferably 2 to 4 hours.

In the polymerization step, the temperature of the polymerization reaction is preferably in the range of 150 to 300 ℃. More preferably, the polymerization temperature is 180 to 290 ℃ and still more preferably 200 to 280 ℃.

Further, the above silane compound, diaryl carbonate and aromatic diol compound have good compatibility with each other, and a polycarbonate copolymer can be produced without using a solvent in the polymerization step. Therefore, the polymerization process can be simplified.

In the polymerization step, the ratio of the molar amount of the transesterification catalyst to the molar amount of the aromatic diol compound (molar ratio, i.e., the value of the molar amount of the transesterification catalyst/the molar amount of the aromatic diol compound) is preferably 1.0 × 10^－7～1.0×10^－2(mol/mol: 0.1 to 10000. mu. mol/mol or 1.0X 10)^－410 mmol/mol). The molar ratio is more preferably 1.0X 10^－7～2.0×10^－5mol/mol (or 0.5 to 20. mu. mol/mol).

In the polymerization step, the molar ratio of the silane compound to the aromatic diol compound (i.e., the value of the number of moles of the silane compound/the number of moles of the aromatic diol compound) is, for example, 0.8 to 1.3, preferably 0.9 to 1.25, and more preferably 0.95 to 1.2.

In the polymerization step, the molar ratio of the total mole number of diaryl carbonate and silane compound to the aromatic diol compound (i.e., the value of (the total mole number of diaryl carbonate and silane compound)/the mole number of aromatic diol compound) is preferably 0.9 to 1.2, and more preferably 0.95 to 1.15.

The polycarbonate copolymer of the present invention will be described in detail below.

< 2. polycarbonate copolymer >

[ (I) structural Unit ]

The polycarbonate copolymer produced by the production method of the present invention is a polymer having a siloxane structural unit as described above, and specific examples thereof include the following polymers.

That is, the polycarbonate copolymer is a polymer having at least a siloxane structural unit represented by any one of the following formulas (1-1) to (1-4) and a polycarbonate structural unit described in detail later.

The group of formulae (1-1) to (1-4) contains R¹And R²The siloxane structure of (2) is introduced from the above-mentioned diaryloxysilane compound, dialkyldialkoxysilane, or silicon compound (siloxane compound).

In the formulae (1-1) to (1-4), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R¹And R²In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

In addition, R¹And R²When the aryl group may have a substituent(s), the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, andthe number of carbon atoms is more preferably 6 to 8.

In the formulae (1-1) and (1-2), R³～R¹⁰And R³⁰～R³³Each independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R³～R¹⁰And R³⁰～R³³In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

R³～R¹⁰And R³⁰～R³³In the case of an alkenyl group which may have a substituent, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

In addition, R³～R¹⁰And R³⁰～R³³In the case of an aryl group which may have a substituent(s), the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

In the formulae (1-1) to (1-3), Z₁And Z₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

In formulae (1-1) to (1-3), J₁And K₁Each independently represents an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, and is, for example, 1 or 2.

In the formula (1-3), A₁And A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3, L₁And L₂Preferably 1 or 2.

In the formulae (1-1) and (1-2), X is independently a single bond or any one of the structural formulae represented by the following formula (2).

In the formula (2), R¹¹And R¹²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R¹¹And R¹²A carbon ring or a heterocycle having 1 to 20 carbon atoms which may have a substituent and which are bonded to each other,

a and b each independently represent 0 or an integer of 1 to 5000.

R¹¹And R¹²Each of which is preferably independently hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent.

In the formula (2), a and b are each independently an integer of 0 or 1 to 5000, and a and b are preferably an integer of 1000 or less, more preferably an integer of 500 or less, and further preferably an integer of 100 or less.

In the siloxane structural unit, X is preferably R¹¹And R¹²A fluorene ring structure formed by bonding to each other.

The siloxane structural unit preferably includes at least a structure represented by the following formula (1).

Containing R in the formula (1)¹And R²The siloxane structure of (2) is introduced from the above-mentioned diaryloxysilane compound, dialkoxysilane or silicon compound (siloxane compound).

In the formula (1), R¹And R²Each independently represents an alkyl group, an alkenyl group or an aryl group which may have a substituent. R in the formula (1)¹And R²Each of which is an alkyl group having 1 to 20 carbon atoms in total or an aryl group having 6 to 30 carbon atoms in total, which may have a substituent.

With respect to R¹And R²And R in the above formulae (1-1) to (1-4)¹And R²The same is true.

As the above-mentioned R¹And R²Examples of the substituent(s) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth) acryloyloxy, glycidoxy and mercapto.

As R in formula (1)¹And R²As preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

In the formula (1), with respect to R³～R¹⁰And R in the above formulae (1-1) to (1-4)³～R¹⁰The same is true.

As the above-mentioned R³～R¹⁰Examples of the substituent(s) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth) acryloyloxy, glycidoxy and mercapto.

In the formula (1), X is the same as X in the formulae (1-1) and (1-2).

The polycarbonate structural unit of the polycarbonate copolymer is represented by any one of the following formulas (3-1) to (3-4).

(3-1) to (3-2) wherein R¹³～R²⁰And R⁴⁰～R⁵¹Each independently represents hydrogen, halogen,An alkoxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R¹³～R²⁰And R⁴⁰～R⁵¹In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

R¹³～R²⁰And R⁴⁰～R⁵¹In the case of an alkenyl group which may have a substituent, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

In addition, R¹³～R²⁰And R⁴⁰～R⁵¹In the case of an aryl group which may have a substituent, the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

In formulae (3-1) to (3-3), Z₃And Z₄Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

In formulae (3-1) to (3-3), J₂And K₂Each independently represents an integer of 0 to 5, preferably 0 to 3, and more preferably 1 or 2.

In the formula (3-3), A₁And A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3, L₁And L₂Preferably 0 to 2.

In the formulae (3-1) to (3-2), Y is independently a single bond or a structural formula represented by the formula (4).

(formula (II)In, R²¹And R²²Each independently represents hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R²¹And R²²A carbocyclic ring or heterocyclic ring having 1 to 20 carbon atoms which may have a substituent and are bonded to each other, and c and d each independently represent 0 or an integer of 1 to 5000.

R²¹And R²²Each of which is preferably independently hydrogen, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 16 carbon atoms which may have a substituent.

In formula (4), c and d are each independently an integer of 0 or 1 to 5000, and c and d are preferably an integer of 1000 or less, more preferably an integer of 500 or less, and still more preferably an integer of 100 or less.

In addition, in the polycarbonate structural unit, Y is preferably R¹¹And R¹²A fluorene ring structure formed by bonding to each other.

The polycarbonate structural unit preferably contains at least a structure represented by the following formula (3).

In the formula (3), R¹³～R²⁰And R in the above formulas (3-1) to (3-2)³～R¹⁰The same is true.

As the above-mentioned R¹³～R²⁰Examples of the substituent(s) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth) acryloyloxy, glycidoxy and mercapto.

In the formula (3), Y is the same as Y in the above-mentioned formulas (3-1) to (3-2).

[ (II) Properties of polycarbonate copolymer ]

The weight average molecular weight of the polycarbonate copolymer is preferably 10000 to 300000, more preferably 10000 to 200000, further preferably 10000 to 100000, for example, more preferably 20000 to 80000, further preferably 30000 to 70000, and particularly preferably 40000 to 65000.

In the polycarbonate copolymer, the number of moles of the siloxane structural unit is preferably 1 to 1000. The number of moles of the polycarbonate structural unit is preferably 1 to 1000. These molar numbers are the number of structural units contained in one molecule of the polycarbonate copolymer, and are preferably 10 to 800, more preferably 100 to 600, respectively.

In the polycarbonate copolymer, the proportion of the siloxane structural unit in the total mole number of the siloxane structural unit and the polycarbonate structural unit is preferably 2.0% or more and 90% or less. The proportion of the siloxane structural unit is more preferably 3.0% or more, for example, more than 3.1% and 90% or less, still more preferably 5% or more and 90% or less, and particularly preferably 8% or more and 90% or less.

In addition, when the polycarbonate copolymer is used in the form of a composition by mixing with another resin, instead of being used alone, it may be preferable to greatly increase the proportion of the siloxane structural unit. For example, the proportion of the siloxane structural unit is 30% or more, 50% or more, or 70% or more, and as described in detail later, by mixing a polycarbonate copolymer having a high Si content with a polymer containing no Si or siloxane structural unit, a resin having excellent properties, for example, high impact resistance and fluidity can be realized. In the application where the proportion of the siloxane structural unit is preferably increased as described above, the upper limit of the proportion of the siloxane structural unit is not limited to 90%, and may be, for example, 92%, 95%, 98%, or the like.

In the polycarbonate copolymer, the molar ratio of the siloxane structural units to the polycarbonate structural units (i.e., the ratio of the number of moles of siloxane structural units to the number of moles of polycarbonate structural units) is preferably 0.01: 99.99 to 99.99: 0.01. The above molar ratio is more preferably 30: 70 to 99.9: 0.01, but may be in other ranges, for example, 1: 99 to 99: 1, 10: 90 to 90: 10, and the like.

In the polycarbonate copolymer, the Q value (melt flow volume per unit time measured at 280 ℃ under a load of 160kg,. times.10^－2cm³s^－1) Preferably, it is8(×10^－2cm³s^－1) The above. The Q value is more preferably 20 (. times.10)^－2cm³s^－1) More preferably 40(× 10) or more^－2cm³s^－1) Above, particularly preferably 60(× 10)^－2cm³s^－1) The above.

In the polycarbonate copolymer, the glass transition temperature (Tg) measured according to JIS K7121 is, for example, 40 to 200 ℃, preferably 45 to 180 ℃, and more preferably 50 to 160 ℃.

In the above-mentioned polycarbonate copolymer, that is, the polycarbonate copolymer having the siloxane structural unit represented by any one of formulae (1-1) to (1-4) and the polycarbonate structural unit represented by any one of formulae (3-1) to (3-4), the low-molecular weight compound having a weight average molecular weight of 1000 or less is preferably 30% by weight or less, more preferably 20% by weight or less, further preferably 10% by weight or less, further preferably 5.0% by weight or less, particularly preferably 1.5% by weight or less, further preferably less than 1.0% by weight. When a polycarbonate copolymer containing a large amount of a low-molecular weight compound having a weight average molecular weight of 1000 or less is continuously subjected to injection molding for producing an optical disk or a complicated and thin-walled product, a mold (molding) tends to be contaminated with a trace amount of deposit (molding deposition) at an early stage. In this regard, in the polycarbonate copolymer, if the amount of the low molecular weight compound having a weight average molecular weight of 1000 or less is less than 1.5 mass%, mold contamination can be effectively prevented.

The lower limit of the content of the low-molecular weight compound having a weight-average molecular weight of 1000 or less in the polycarbonate copolymer is about 0.7% by weight, although not particularly critical. Even when the low molecular weight compound is contained in an amount of about 0.001 wt%, 0.01 wt%, or 0.1 wt% or more, the properties of the polycarbonate copolymer are not problematic particularly when used for optical applications, and the effect of improving the flowability can be confirmed. Therefore, the lower limit of the content of the low-molecular weight compound having a weight-average molecular weight of 1000 or less in the polycarbonate copolymer may be 0.001 wt%, 0.01 wt%, or 0.1 wt%.

As will be described in detail in examples later, the content of the low-molecular weight compound in the polycarbonate copolymer is a value calculated by adding the contents of several low-molecular weight compounds as impurities based on the peak area ratio of each component obtained by GPC analysis. That is, as described in detail later, the proportion of the low molecular weight compound having a molecular weight of 1000 or less in the polycarbonate copolymer is a value calculated from the ratio of the area up to a retention time of 20.5min to 21.5 min/the area up to 0min to 21.5min under the conditions of a predetermined GPC analysis.

In the polycarbonate copolymer described above, that is, the polycarbonate copolymer having the siloxane structural unit represented by any one of formulae (1-1) to (1-4) and the polycarbonate structural unit represented by any one of formulae (3-1) to (3-4), the total content of the cyclic bodies represented by formulae (5-1) to (5-3) below is preferably 4.0% by weight or less, more preferably 3.0% by weight or less, even more preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less, based on the total weight of the polycarbonate copolymer.

When the content of the cyclic dimer is within the above range, it can be said that the properties of the polycarbonate copolymer, particularly when used for optical applications, are not problematic.

In the formulae (5-1) to (5-3), m and n represent the content of (-OSi (R) in each ring body₁R₂) The total number of structural units in the O-) site, and the total number of structural units including the (-OC (═ O) O-) site. That is, in the formula (5-1)The ring body includes a compound other than (-OSi (R)₁R₂) In the case of a structural unit other than a structural unit of an O-) site, and in the case where a structural unit other than a structural unit containing a (-OC (═ O) O-) site is included in the annular body of formula (5-2), m and n each represent the total number of structural units represented by the formula in the annular body. In particular, formula (5-3) further includes a compound containing (-OSi (R)₁R₂) In the case of cyclic bodies in which a structural unit having an O-) site and a structural unit having a (-OC (═ O) O-) site are mixed, for example, and these are alternately arranged, m and n also represent the total number of structural units represented by the formulae in the cyclic body.

In the formula (5-1), m represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and further preferably 2.

In the formula (5-2), n represents an integer of 2 to 10, preferably 2 to 5, more preferably 2 or 3, and further preferably 2.

In the formula (5-3), the sum of m values is 1 to 10, and the sum of n values is 1 to 10. M and n are each preferably 1 to 5, more preferably 1 or 2, and still more preferably 1.

In the formula (5-3), as described above, (-OSi (R) (-OSi) (R) (-OSi (R)) is contained in the cyclic body of the formula (5-3)₁R₂) The arrangement of the structural unit containing an O — (OC (═ O) O-) site and the structural unit containing an O —.

In the formulae (5-1) to (5-3), X₁And X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

i and ii each independently represent an integer of 0 to 5, preferably 0 to 3, and more preferably 1 or 2.

In the formulae (5-1) to (5-3), R¹、R²、R³～R¹⁰、R¹³～R²⁰And X is respectively reacted with R in the formulae (1-1) and (1-2)¹、R²、R³～R¹⁰、R¹³～R²⁰The same as X.

Specific examples of the compounds of the formulae (5-1) to (5-3) include the following cyclic compounds of the formulae (5-1 ') to (5-3').

In formula (5-1'), m is 2 or 3, preferably m is 2; in formula (5-2'), n ═ 2 or 3, preferably n ═ 2; in the formula (5-3'), m is any one of 1 to 3, and n is any one of 1 to 3, preferably 1 or 2, and more preferably 1.

The polycarbonate copolymer may contain the total content of the cyclic bodies represented by the following formulae (6-1) and (6-2). These cyclic bodies are considered to be cyclic dimers formed by a side reaction of the polymerization reaction for producing the polycarbonate copolymer. The total content of these cyclic dimers in the polycarbonate copolymer is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, further preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less, based on the total weight of the polycarbonate copolymer.

In the formulae (6-1) and (6-2), R¹、R²、R³～R¹⁰、R³⁰～R³³And X is the same as in the formulae (1-1) and (1-2).

In the formulae (6-1) and (6-2),

X₁and X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

i and ii each independently represent an integer of 0 to 5, preferably 0 to 3, and more preferably 1 or 2.

n represents an integer of 2 to 10, preferably an integer of 2 to 5, more preferably 2 or 3, for example 2.

The lower limit of the total content of the cyclic dimer represented by the formulae (6-1) and (6-2) contained in the polycarbonate copolymer is not particularly limited, and may be, for example, 0.001 wt%, 0.01 wt%, or 0.1 wt%. The presence of a certain amount of the cyclic dimer contributes to the improvement of the flowability of the polycarbonate copolymer at the time of molding.

Specific examples of the compounds of the formulae (6-1) and (6-2) include the following cyclic compounds of the formulae (6-1 ') and (6-2').

Wherein R in the formulae (6-1 ') and (6-2')¹And R²、R³～R¹⁰And R³⁰～R³³、Z₁And Z₂、J₁、K₁And X is as described above.

In the polycarbonate copolymer, the thermal decomposition temperature reduced by 1% by mass is preferably 415 ℃ or less, more preferably the thermal decomposition temperature reduced by 1% by mass is 400 ℃ or less, still more preferably the thermal decomposition temperature reduced by 1% by mass is 385 ℃ or less, and particularly preferably the thermal decomposition temperature reduced by 1% by mass is 370 ℃ or less.

In the polycarbonate copolymer, the proportion of the total weight of silicon atoms (total Si amount) is preferably 0.1 to 20 mass%, more preferably 1.0 to 15 mass%, even more preferably 2.0 to 12 mass%, and particularly preferably 3.0 to 10 mass% (for example, 3.1 mass% or more, or more than 3.1 mass% and 9.8 mass% or less), based on the total weight of the polycarbonate copolymer.

The composition of the present invention, that is, the composition containing the polycarbonate copolymer and the like will be described in detail below.

< 3. composition >

The composition of the present invention contains the above polycarbonate copolymer and a polycarbonate resin which is not the above polycarbonate copolymer. Examples of the polycarbonate resin that does not belong to the polycarbonate copolymer include a polycarbonate resin that does not contain any siloxane structure at all or substantially does not contain any siloxane structure.

The kind of the polycarbonate resin which does not belong to the polycarbonate copolymer is not particularly limited as long as it contains a [ O-R-OCO ] -unit containing a carbonate bond in the molecular main chain (R is a group containing an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group and having a linear structure or a branched structure). Further, the polycarbonate resin not belonging to the above polycarbonate copolymer may not contain a polyester carbonate. In addition, the same applies to polyestercarbonates as long as they contain a [ O-R-OC ] -unit containing a carbonate bond in the main chain of the molecule (R is as defined above), and there is no particular limitation.

The weight average molecular weight of the polycarbonate resin is preferably 10000 to 100000, more preferably 13000 to 80000, and further preferably 15000 to 60000.

The composition of the present invention may contain a resin other than the polycarbonate resin, and is preferably a thermoplastic resin. The kind of the thermoplastic resin is not particularly limited, and examples thereof include, in addition to polycarbonate resins and polyester carbonate resins, acrylic resins such as polymethyl methacrylate (PMMA), various resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), Polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyethersulfone, cellophane, and aromatic polyamide.

The total weight of silicon atoms (total Si content) in the composition is preferably 0.1 to 20 mass%, more preferably 0.2 to 15 mass%, and particularly preferably 0.3 to 10 mass%, based on the total weight of the composition. The proportion of the total Si amount in the composition can be adjusted by the proportion of the siloxane structural unit in the polycarbonate resin in the total structural units, or the amount of the resin mixed with the polycarbonate resin or the Si amount.

For example, the Q value Q of a composition containing a polycarbonate copolymer measured at 280 ℃ and 160kgf₁And a Q value measured under the same conditions only for the polycarbonate resin contained in the composition₂In contrast, the value is preferably 120% or more (20% or more higher), and the Q of the entire composition₁Value of Q of polycarbonate only₂The value is more preferably 130% or more, still more preferably 140% or more, particularly preferably 150% or more, for example, 160% or more.

Further, for example, in the case of a composition containing 5% by mass of a polycarbonate copolymer, the Q value Q measured under the conditions of 280 ℃ and 160kgf₁And a Q value measured under the same conditions only for the polycarbonate resin contained in the composition₂In contrast, the value is preferably 140% or more (40% or more higher), and the Q of the whole composition₁Value of Q of polycarbonate only₂The value is more preferably 150% or more, still more preferably 160% or more, particularly preferably 170% or more, for example, 180% or more.

The use of a polycarbonate copolymer with a high Si content enables the manufacture of compositions with excellent characteristics. By mixing a polycarbonate copolymer or the like having an Si content of, for example, 0.1 mass% or more with a resin substantially not containing a siloxane structural unit, preferably a polycarbonate resin, the obtained composition can have both excellent impact resistance and fluidity.

The composition containing the polycarbonate copolymer may contain a phenolic compound produced as a by-product of the polymerization reaction, a silane compound remaining unreacted, a carbonate compound and a diol compound. The phenol compound or DPC as an impurity also causes a decrease in strength and generation of odor when formed into a molded article, and therefore, the content thereof is preferably as small as possible. Therefore, the content of the phenolic compound, the silane compound, the carbonate compound and the diol compound can be reduced to be undetectable, but can be included in the composition within a range that does not impair the effect from the viewpoint of productivity. Further, by containing a predetermined amount of the monomer residue, for example, 1 to 1000 ppm by weight, preferably 10 to 900ppm by weight, and more preferably 20 to 800ppm by weight based on the total weight of the composition, the effect of improving the fluidity at the time of molding can be obtained, and the plasticity at the time of melting the resin is good.

The molded article of the present invention comprising a polycarbonate copolymer will be described below.

< 4. shaped article

The molded article of the present invention is obtained by molding the polycarbonate copolymer or a composition containing the polycarbonate copolymer. The method of molding the molded article is not particularly limited, and examples of the molded article include injection molded articles, press molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and pressure-air molded articles.

The optical lens and the molded article of the present invention are obtained by molding the polycarbonate copolymer of the present invention, a composition containing the polycarbonate copolymer, or the like. The polycarbonate copolymer of the present invention is suitable for optical applications, and the optical lens of the present invention has a refractive index, an abbe number, and the like in a range suitable for use as a lens.

[ II. polysiloxane Compound ]

The method for producing a polysiloxane compound such as polyarylene siloxane of the present invention includes a polymerization step of polymerizing an oxysilane compound such as a predetermined diaryloxysilane compound and a diol compound such as an aromatic diol compound in the presence of a transesterification catalyst, both of which are described in detail later. The following describes a method for producing a polysiloxane compound.

In the method for producing a polysiloxane compound, the raw materials, reaction conditions, and the like described for the polycarbonate copolymer can be used, and the raw materials, reaction conditions, and the like described for the method for producing a polysiloxane compound can be used in the method for producing a polycarbonate copolymer.

The above polymerization reaction is summarized as follows. For example, a diphenoxysilane compound (Si (CH) having 2 methyl groups and phenoxy groups as an example of a diaryloxysilane compound₃)₂(OPh)₂) When reacted with bisphenol A, which is an example of an aromatic diol compound, the following polyarylene siloxane compound was obtained.

That is, a polyarylene siloxane compound having a siloxane structure produced by the reaction of the following formula (a) can be produced.

In this polymerization reaction, an aryl alcohol such as phenol (PhOH) is produced as a by-product as described below. Therefore, in the polymerization step, the polymerization reaction is carried out while removing the aryl alcohol as a by-product such as phenol under reduced pressure in a state where the mixture of the above components is melted.

The process for producing the polysiloxane compound of the present invention will be described in detail below. The polysiloxane compound includes a polyarylene siloxane compound, a polyalkylene siloxane compound, a mixture thereof, and a form in which a structural unit derived from a diaryloxysilane compound and a structural unit derived from a dialkoxysilane, which are described in detail later, are included in a polymer chain.

< 1. method for producing polysiloxane Compound

[ (I) oxysilane Compound ]

Examples of the oxysilane compound used for producing the polysiloxane compound include a diaryloxysilane compound and a dialkoxysilane.

(A-1) Diaryloxysilane Compound

For example, as shown in the above formula (A), a diaryloxysilane compound used in the polymerization step is used to form the siloxane structural unit in the polyarylene siloxane compound.

In the diaryloxysilane compound represented by the general formula Si (R)^aR^b)(OAr)₂When is represented, R^aAnd R^bEach independently selected from alkyl and aryl. R^aAnd R^bEach independently preferably has a substituent(s) selected from the group consisting of alkyl groups having 1 to 20 carbon atoms in total and aryl groups having 6 to 30 carbon atoms in total. More preferably in R^aAnd R^bIn the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 or 2.

In addition, R^aAnd R^bIn the case of an aryl group which may have a substituent(s), the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

As R in formula (1)^aAnd R^bAs preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

Further, it is also known from the above formula (A) that the aryloxy group (OAr group) of the diaryloxysilane compound forms a by-product (ArOH) such as phenol, for example, and is not introduced into the polymer chain of the polyarylene siloxane compound. Therefore, the kind of the aryloxy group is not particularly limited. However, in order to remove the by-product in the polymerization step from the reaction system as easily as possible, the aryloxy group is preferably low in polarity and molecular weight, and is, for example, a phenoxy group.

These diaryloxysilane compounds can be synthesized by a known method, and commercially available products can be used.

(A-2) dialkoxysilanes

In the dialkoxysilanes of the general formula Si (R)^aR^b)(OR^c)₂When is represented, R^aAnd R^bEach independently with R described in (A-1) diaryloxysilane compound^aAnd R^bLikewise selected from alkyl and aryl groups.

Further, from the above formula (A), alkoxy group (OR) of silane compound^cRadical) generates by-products (MeOH) such as methanol without being introduced into the polymer chains of the polycarbonate copolymer. Therefore, the kind of the alkoxy group is not particularly limited. However, in order to remove the by-product in the polymerization step from the reaction system as easily as possible, an alkoxy group (OR)^cRadical) is, for example, methoxy.

[ (II) diol Compound ]

Examples of the diol compound used for producing the polysiloxane compound include an aromatic diol compound and an alicyclic diol compound. As the diol compound, a mixture of an aromatic diol compound and an alicyclic diol compound may be used.

(A-1) aromatic diol Compound

As shown in the above formula (a) regarding the general polymerization reaction, the aromatic diol compound used in the polymerization step is used to constitute the main chain of the polysiloxane compound such as a polyarylene siloxane compound.

In addition, the polycarbonate copolymer of the [ (III-1) aromatic diol compound ] described in the aromatic diol compound can also be used in the production of polysiloxane compounds polymerization process.

(A-2) alicyclic diol Compound

The alicyclic diol compound used in the polymerization step can also be used to constitute the main chain of the polysiloxane compound.

Specific examples of the alicyclic diol compound include spiroglycol, cyclohexanedimethanol, PCPDM, TCDDM, and the like.

In addition, the alicyclic diol compound described in the above [ (III-2) alicyclic diol compound ] relating to the polycarbonate copolymer can also be used in the polymerization step for producing the polysiloxane compound.

[ (III) transesterification catalyst ]

The transesterification catalyst used in the polymerization step is preferably a catalyst containing a basic compound. Examples of the basic compound catalyst include catalysts containing an alkali metal compound, an alkaline earth metal compound, and the like, and examples of such compounds include organic acid salts such as alkali metal and alkaline earth metal compounds, inorganic salts such as carbonates, oxides, hydroxides, hydrides, alkanols, and the like. Alternatively, as the basic compound catalyst, quaternary ammonium bases, salts thereof, amines, and the like can be used. In addition, these compounds may be used alone or in combination of plural kinds.

Among the above basic compound catalysts, the transesterification catalyst more preferably contains an alkali metal carbonate or an alkali metal hydroxide. Specific examples of more preferable transesterification catalysts include catalysts containing cesium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium hydroxide, potassium hydroxide, sodium hydroxide, and the like.

The transesterification catalyst may be prepared by a known method, or a commercially available product may be used.

[ (IV) polymerization Process ]

In the polymerization step, at least the dioxysilane compound such as the diaryloxysilane compound (I) and the diol compound such as the aromatic diol compound (II) are polymerized in the presence of the transesterification catalyst (III). In this polymerization reaction, the mixture of the above components is melted to form a molten state, and the aryl alcohol and/or alkyl alcohol as a by-product is removed under reduced pressure. By setting the reaction conditions in this manner, the polymerization reaction can be efficiently performed.

In the polymerization step, the pressure in the polymerization reaction is preferably in the range of 101,300Pa or less. The pressure of the polymerization reaction is more preferably 27,000Pa or less, and still more preferably 400Pa or less.

In the polymerization step, it is preferable to maintain a state of normal pressure not reduced in pressure or a state of reduced pressure less than a certain degree of time, and then gradually reduce the pressure in the system to further perform the polymerization reaction. By gradually increasing the degree of reduced pressure in the reaction system from the middle, the operation necessary for initiating the reaction can be started at normal pressure, and the aryl alcohol or alkyl alcohol as a by-product can be easily removed from the reaction system. Specifically, the pressure reduction step is preferably performed at a rate of about 100 to 10,000 Pa/min, more preferably 500 to 7,000 Pa/min, and still more preferably 1000 to 4,000 Pa/min.

As is clear from the above description, in the polymerization step, it is not generally necessary to carry out the polymerization reaction under reduced pressure, but it is preferable to carry out the polymerization reaction to some extent from a state in which at least the raw materials are in a molten state, and then reduce the pressure in the reaction system. For example, since the reaction temperature is gradually raised in the polymerization step as described later, the depressurization step is preferably started after the temperature of the reaction system is raised to a certain extent, for example, in a state where the temperature is raised to 150 ℃ or higher, more preferably 180 ℃ or higher.

In the polymerization step, the temperature in the polymerization reaction is preferably in the range of 150 to 300 ℃. The polymerization temperature is more preferably 180 to 290 ℃ and still more preferably 200 to 280 ℃.

In this way, in the polymerization step, it is preferable to polymerize the oxysilane compound or diaryloxysilane compound and the diol compound or aromatic diol compound at a reaction temperature higher than 200 ℃. Further, it is preferable to carry out the polymerization step under reduced pressure.

In order to gradually produce and remove the aryl alcohol or alkyl alcohol as a by-product, it is preferable to gradually raise the temperature from room temperature to a reaction temperature set within the above range, for example. The temperature is preferably raised at a rate of about 1 to 10 ℃/min, more preferably 2 to 8 ℃/min, and still more preferably 3 to 7 ℃/min.

The time of the polymerization step is also appropriately set in consideration of the reaction conditions such as the type, pressure, and temperature of the intended polysiloxane compound, and for example, the total time taken for the polymerization step is within 1 to 10 hours. More specifically, the reaction time before the pressure reduction in the reaction system is 0.1 to 3 hours, preferably 0.5 to 2 hours, and the reaction time after the pressure reduction is 0.5 to 8 hours, preferably 1 to 6 hours.

Further, the above-mentioned oxysilane compound and diol compound have good compatibility with each other, and a polycarbonate copolymer can be produced without using a solvent in the polymerization step. Therefore, a solvent such as a halogen-based solvent is not required, and therefore, the environmental load due to the polymerization reaction can be reduced and the polymerization process can be simplified.

The by-products produced in the polymerization step are the above-mentioned aryl alcohol, alkyl alcohol and the like, and are easily removed from the reaction system, and special treatment is not required in consideration of safety and the like. Therefore, the method for producing a polysiloxane compound of the present invention can reduce the environmental load as compared with a conventional production method in which an acid is produced as a by-product or used.

In the polymerization step, the ratio of the molar amount of the transesterification catalyst to the molar amount of the aromatic diol compound (molar ratio, i.e., the value of the molar amount of the transesterification catalyst to the molar amount of the aromatic diol compound) is 0.01 to 16000. mu. mol/mol (1.0X 10)^－8～1.6×10^－2). The molar ratio isPreferably 0.05 to 10000. mu. mol/mol (5.0X 10)^－8～1.0×10^－2) More preferably 0.5 to 5000. mu. mol/mol (5.0X 10)^－7～5.0×10^－3) More preferably 0.80 to 1000. mu. mol/mol (8.0X 10)^－7～1.0×10^－3) Particularly preferably 1.0 to 100. mu. mol/mol (1.0X 10)^－6～1.0×10^－4)。

In the polymerization step, the molar ratio of the oxysilane compound such as a diaryloxysilane compound to the diol compound such as an aromatic diol compound (i.e., the value of the number of moles of the oxysilane compound per mole of the diol compound) is, for example, 0.8 to 1.3, preferably 0.9 to 1.2, more preferably 0.95 to 1.18, and still more preferably 1.00 to 1.16.

The silicone compound of the present invention is explained in detail below.

[ (V) polysiloxane Compound ]

The polysiloxane compound produced by the production method of the present invention is a polymer having a siloxane structural unit as described above, and specific examples thereof include the following polymers.

That is, the polyarylene siloxane compound is a polymer having at least a siloxane structural unit represented by any one of the following formulas (1-1 ') to (1-4').

Formula (1-1') - (1-4 ') in (4'), R¹And R²Each independently represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R¹And R²In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

In addition, R¹And R²In the case of an aryl group which may have a substituent(s), the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

In the formulae (1-1 ') and (1-2'), R³～R¹⁰Each independently represents hydrogen, halogen, alkoxy, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R³～R¹⁰In the case of an alkyl group which may have a substituent, the total number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and particularly preferably 1 or 2.

R³～R¹⁰In the case of an alkenyl group which may have a substituent, the total number of carbon atoms is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

In addition, R³～R¹⁰In the case of an aryl group which may have a substituent(s), the total number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and particularly preferably 6 to 8.

In the formulae (1-1 ') to (1-3'), Z₁Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

In the formulae (1-1 ') to (1-3'), J₁And K₁Each independently represents an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2For example 1 or 2.

In the formula (1-3'), A₁And A₂Each independently represents any one of-O-, -CH-,

L₁and L₂Each independently represents an integer of 0 to 3, L₁And L₂Preferably 1 or 2.

In the formulae (1-1 ') and (1-2'), X is independently a single bond or any of the structural formulae represented by the following formula (2).

a and b each independently represent 0 or an integer of 1 to 5000.

In the siloxane structural unit, X is preferably R¹¹And R¹²A fluorene ring structure formed by bonding to each other.

The siloxane structural unit preferably contains at least a structural unit represented by the following formula (1').

Containing R in formula (1¹And R²The siloxane structure of (a) is introduced from the above-mentioned oxysilane compound.

In the formula (1'), with respect to R¹And R²And R in the above formulae (1-1 ') to (1-4')¹And R²The same is true.

As the above-mentioned R¹And R²Examples of the substituent(s) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth) acryloyloxy, glycidoxy and mercapto.

As R in formula (1')¹And R²As preferable specific examples thereof, methyl group, phenyl group, vinyl group and propyl group can be cited.

In the formula (1'), with respect to R³～R¹⁰And R in the above formulae (1-1 ') to (1-4')¹And R²The same is true.

As the above-mentioned R³～R¹⁰Examples of the substituent(s) include hydroxyl, halogen, amino, vinyl, carboxyl, cyano, (meth) acryloyloxy, glycidoxy and mercapto.

In the formula (1'), m represents an integer of 10 to 1000. The value of m in formula (1') is preferably 20 to 800, more preferably 30 to 500.

In the formula (1), X is the same as R in the above-mentioned formulae (1-1 ') and (1-2')¹And R²The same is true.

The weight average molecular weight of the polysiloxane compound such as polyarylene siloxane compound is preferably 5000 to 300000, more preferably 10000 to 300000, further preferably 10000 to 200000, particularly preferably 10000 to 100000, for example 20000 to 90000, further preferably 30000 to 80000, particularly preferably 40000 to 70000.

Among polysiloxane compounds such as polyarylene siloxane compounds, the glass transition temperature (Tg) measured according to JIS K7121 is, for example, 40 to 200 ℃, preferably 45 to 160 ℃.

In the polysiloxane compound having a siloxane structural unit represented by any one of the formulae (1-1) to (1-4) and (1-1 ') to (1-4'), the weight average molecular weight is preferably 5000 to 300000, and the total content of the cyclic bodies represented by the following formula (5-4) is preferably 4.0% by weight or less, more preferably 3.0% by weight or less, further preferably 2.0% by weight or less, and particularly preferably 1.0% by weight or less, based on the total weight of the polysiloxane compound.

When the total content of these cyclic bodies having a small molecular weight, for example, cyclic dimers is within the above range, it can be said that the properties of the silicone compound are good, particularly when used for optical applications.

In the formula (5-4), the arrangement of the structural unit represented by the formula (5-4) and other structural units is arbitrary. That is, although structural units other than the structural unit whose structure is explicitly represented by the formula (5-4) may be included, the total value of m is 2 to 10, preferably 2 to 5, more preferably 2 or 3, for example, 2 in any case.

R¹、R²、R³～R¹⁰And X is the same as the group of the formula (1-1) or the formula (1-2).

In the formula (5-4), X₁And X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

In the formula (5-4), i and ii each independently represent an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, for example, 1 or 2.

The lower limit of the content of the cyclic product having a small molecular weight in the polysiloxane compound is not particularly limited, but may be about 0.7% by weight, as in the case of the low-molecular-weight compound having a weight average molecular weight of 1000 or less in the polycarbonate copolymer. Among these, even when the low molecular weight compound is contained in an amount of about 0.001 wt%, 0.01 wt%, or 0.1 wt% or more, the properties of the polysiloxane compound, particularly when used for optical applications, are not problematic, and the fluidity is improved. Therefore, the lower limit of the content of the low-molecular weight compound having a weight-average molecular weight of 1000 or less in the polysiloxane compound may be 0.001 wt%, 0.01 wt%, or 0.1 wt%.

The content of the low-molecular-weight cyclic body in the polysiloxane compound is calculated by adding the contents of the several low-molecular-weight compounds as impurities based on the peak area ratios of the respective components obtained by GPC analysis, as described later in detail in examples. That is, as described in detail later, the ratio of the low molecular weight compound having a molecular weight of 1000 or less in the polycarbonate copolymer can be calculated from a predetermined GPC area ratio in the same manner as the measurement of the ratio of the low molecular weight compound having a molecular weight of 1000 or less in the polycarbonate copolymer.

Among them, the cyclic body represented by the formula (5-4) includes, as a specific example, a cyclic dimer represented by the following formula (5-4 '), and it can be confirmed that the molecular structure of the cyclic dimer represented by the formula (5-4') and the polysiloxane compound contain such a cyclic dimer.

The polysiloxane compound may contain the total content of the cyclic compounds represented by the following formulae (6-1) and (6-2). It is considered that these cyclic bodies form cyclic dimers due to side reactions in the polymerization reaction for producing the polysiloxane compound. The content of these cyclic dimers in the silicone compound is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, further preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less, based on the total weight of the silicone compound.

In the formulae (6-1) and (6-2), the arrangement of the structural unit represented by these formulae and other structural units is arbitrary. That is, although structural units other than the structural units whose structures are explicitly represented by the formulae (6-1) and (6-2) may be included, the total value of n is 2 to 10, preferably 2 to 5, more preferably 2 or 3, for example, 2 in any case.

In the formulae (6-1) and (6-2), X₁And X₂Each independently an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 or 2 carbon atoms.

In the formulae (6-1) and (6-2), i and ii each independently represent an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, for example, 1 or 2.

Wherein R in the formulae (6-1) and (6-2)¹And R²、R³～R¹⁰、Z₁And Z₂、J₁、K₁And X is as described above.

The lower limit of the total content of the cyclic dimers represented by the formulae (6-1) and (6-2) contained in the silicone compound is not particularly limited, and may be, for example, 0.001 wt%, 0.01 wt%, or 0.1 wt%. The presence of a certain amount of cyclic dimer contributes to the improvement in flowability of the polycarbonate polysiloxane compound at the time of molding.

Specific examples of the compounds of the formulae (6-1) and (6-2) include the following cyclic compounds of the formulae (6-1 ') and (6-2').

Wherein R in the formulae (6-1 ') and (6-2')¹And R²、R³～R¹⁰And R³⁰～R³³、Z₁And Z₂、J₁、K₁And X is as described above.

In the polysiloxane compound, the thermal decomposition temperature reduced by 1% by mass is preferably 415 ℃ or less, more preferably the thermal decomposition temperature reduced by 1% by mass is 400 ℃ or less, still more preferably the thermal decomposition temperature reduced by 1% by mass is 385 ℃ or less, and particularly preferably the thermal decomposition temperature reduced by 1% by mass is 370 ℃ or less.

In the polysiloxane compound, the proportion of the total weight of silicon atoms (total Si amount) is preferably 0.1 to 20 mass%, more preferably 1.0 to 15 mass%, even more preferably 2.0 to 12 mass%, and particularly preferably 3.0 to 10 mass% (for example, 3.1 mass% or more, or more than 3.1 mass% and 9.8 mass% or less), based on the total weight of the polysiloxane compound.

The composition of the present invention, that is, the composition containing the polysiloxane compound and the like, will be described in detail below.

< 3. composition >

The composition of the present invention contains the polysiloxane compound and a polycarbonate resin. Examples of the polycarbonate resin include polycarbonate resins containing no siloxane structure at all or containing substantially no siloxane structure.

The kind of the polycarbonate resin to be contained in the composition together with the polysiloxane compound is not particularly limited as long as it contains a unit of- [ O-R-OCO ] -having a carbonate bond in the molecular main chain (R is a group containing an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group and having a linear structure or a branched structure). In addition, polycarbonate resins that do not belong to the polysiloxane compounds described above may not include polyestercarbonates. The polyester carbonate is not particularly limited as long as it is a unit of- [ O-R-OC ] -having a carbonate bond in the main chain of the molecule (R is as described above).

The weight average molecular weight of the polycarbonate resin contained in the composition together with the polysiloxane compound is preferably 10000 to 100000, more preferably 13000 to 80000, and further preferably 15000 to 60000.

The composition of the present invention may contain a resin other than the polycarbonate resin, and preferably contains a thermoplastic resin. The kind of the thermoplastic resin is not particularly limited, and examples thereof include acrylic resins such as polymethyl methacrylate (PMMA), various resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), Polyimide (PI), cycloolefin copolymer (COC), norbornene-containing resins, polyethersulfone, cellophane, and aromatic polyamide, in addition to polycarbonate resins and polyester carbonate resins.

For example, the Q value Q of a composition containing a silicone compound measured at 280 ℃ and 160kgf₁And a Q value measured under the same conditions only for the polycarbonate resin contained in the composition₂In contrast, the value is preferably 120% or more (20% or more higher), and the Q of the entire composition₁Value of Q of polycarbonate only₂The value ratio is preferably 130% or more, more preferably 140% or more, particularly preferably 150% or more, for example, 160% or more.

Further, for example, a composition containing 5% by mass of a silicone compound has a Q value Q measured at 280 ℃ and 160kgf₁And a Q value measured under the same conditions only for the polycarbonate resin contained in the composition₂In contrast, the value is preferably 140% or more (40% or more higher), and the Q of the whole composition₁Value of Q of polycarbonate only₂The value ratio is preferably 150% or more, more preferably 160% or more, particularly preferably 170% or more, for example, 180% or more.

The use of a polysiloxane compound having a high Si content enables the production of a composition having excellent characteristics. By mixing a polysiloxane compound or the like having an Si content of, for example, 0.1 mass% or more with a resin substantially not containing a siloxane structural unit, preferably a polycarbonate resin, the obtained composition can have both excellent impact resistance and fluidity.

The composition containing the polysiloxane compound may contain a phenolic compound produced as a by-product of the polymerization reaction, an unreacted and remaining oxysilane compound, and a diol compound. The phenol compound or DPC as an impurity also causes a decrease in strength and generation of odor when formed into a molded article, and therefore, the content thereof is preferably as small as possible. Therefore, the content of the phenolic compound, the oxysilane compound, and the diol compound can be reduced to be undetectable, but can be included in the composition within a range that does not impair the effect from the viewpoint of productivity. Further, by containing a predetermined amount of the monomer residue, for example, 1 to 1000 ppm by weight, preferably 10 to 900ppm by weight, and more preferably 20 to 800ppm by weight based on the total weight of the composition, the effect of improving the fluidity at the time of molding can be obtained, and the plasticity at the time of melting the resin is good.

< 4. shaped article

Next, a molded article comprising a polysiloxane compound such as the above-mentioned polyarylene siloxane compound will be described.

The molded article of the present invention is obtained by molding the above-mentioned polysiloxane compound such as polyarylene siloxane compound. The method of molding the molded article is not particularly limited, and examples of the molded article include injection molded articles, press molded articles, blow molded articles, extrusion molded articles, vacuum molded articles, and pressure-air molded articles.

The optical lens of the present invention is obtained by molding the silicone compound of the present invention or a composition containing the silicone compound. The polysiloxane compound of the present invention is suitable for optical applications, and is suitably used for optical films, optical lenses, and the like. The optical lens of the present invention has a refractive index, abbe number, and the like in a range suitable for use as a lens.

(regarding minor ingredients)

Inactivating agent

In the polycarbonate copolymer and the polysiloxane compound of the present invention, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolytic stability after the completion of the polymerization reaction. It is preferable to carry out a method of deactivating the catalyst by adding a known acidic substance. As the acidic substance, specifically, there are suitably used: esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; phosphoric acid esters such as triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid; phosphonic acid esters such as diethyl phenylphosphonate; phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonic acid salts such as tetrabutylphosphonium dodecylbenzenesulfonate; organic halides such as stearoyl chloride, benzoyl chloride, p-toluenesulfonyl chloride and the like; alkyl sulfuric acids such as dimethyl sulfuric acid; organic halides such as benzyl chloride, and the like. The amount of the deactivator is, for example, 0.001 to 50 times by mol, preferably 0.01 to 30 times by mol, based on the amount of the catalyst.

Additive agent

< stabilizer >

Stabilizers may be added to the polycarbonate copolymer and polysiloxane compound of the present invention. Examples of the stabilizer include a heat stabilizer and an antioxidant. The proportion of the stabilizer added is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and even more preferably 0.02 part by mass or more, and is preferably 2 parts by mass or less, more preferably 1.4 parts by mass or less, and even more preferably 1.0 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound. The stabilizer may contain only 1 kind, or may contain 2 or more kinds. When 2 or more species are contained, the total amount preferably falls within the above range.

Thermal stabilizer

Examples of the heat stabilizer include phenol-based, phosphorus-based, and sulfur-based heat stabilizers. Specific examples thereof include: phosphorus oxyacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acid metal pyrophosphate such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of group 1 or group 10 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate ester compounds, organic phosphite ester compounds, organic phosphonate ester compounds, and the like. Further, at least 1 kind selected from the group consisting of a phosphite ester compound (a) in which at least 1 ester in the molecule is esterified with phenol and/or phenol having an alkyl group of at least 1 carbon atom number of 1 to 25, a phosphorous acid (b), and a tetrakis (2, 4-di-t-butylphenyl) -4, 4' -biphenylene-diphosphonate ester (c) can be cited. Specific examples of the phosphite compound (a) include trioctyl phosphite, trioctadecyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl/dinonyl-phenyl) phosphite, trinonylphenyl phosphite, trioctylphenyl phosphite, tris (2, 4-di-t-butylphenyl) phosphite, trinonyl phosphite, didecylmonophenyl phosphite, dioctylmonophenyl phosphite, diisopropyl monophenyl phosphite, monobutyldiphenyl phosphite, monodecyl diphenyl phosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, tris (nonyl/dinonyl-phenyl) phosphite, tris (2, 4-t-butylphenyl) phosphite, tris (octylphenyl) phosphite, bis (6-t-butyl-4-methylphenyl) pentaerythritol phosphite, tris (2, tris (6-t-butyl-4-methylphenyl) phosphite, tris (t-butyl-4-phenyl) phosphite, tris (n-butyl-phenyl) phosphite, tris (p-butyl-phenyl) phosphite, n-butyl-phenyl) phosphite, and the like, Monooctyldiphenyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, diphenyl pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-methylenebis (4, 6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, and the like. These may be used alone, or 2 or more of them may be used in combination.

Examples of the organic phosphite compound include "ADK STAB 1178 (trade name, the same below)" produced by ADEKA CORPORATION, "ADK STAB 2112", "ADK STAB HP-10", "JP-351", "JP-360", "JP-3 CP" produced by North City chemical industry Co., Ltd, "Irgafos 168" produced by BASF CORPORATION.

Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, and 2-ethylphenyldiphenyl phosphate.

The proportion of the heat stabilizer to be added is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and still more preferably 0.03 part by mass or more, and preferably 1 part by mass or less, more preferably 0.7 part by mass or less, and still more preferably 0.5 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound.

The heat stabilizer may contain only 1 kind, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is within the above range.

[ antioxidant ]

Examples of the antioxidant include a phenol-based antioxidant, a hindered phenol-based antioxidant, a bisphenol-based antioxidant, and a polyphenol-based antioxidant. Specific examples thereof include 2, 6-di-tert-butyl-4-methylphenol, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, n-octadecyl-3- (3 ',5' -di-tert-butyl-4 '-hydroxyphenyl) propionate, tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 4' -butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ], 3, 9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro [5,5] undecane, pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N ' -hexane-1, 6-diylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenylpropionamide) ], 2, 4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] phosphate, 3',5, 5', 5 '-hexa-tert-butyl-a, a', a' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, 4, 6-bis (octylthiomethyl) o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate ], hexamethylenebis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2, 6-di-tert-butyl-4- (4, 6-bis (octylthio) -1,3, 5-triazine-2-ylamino) phenol and the like.

Examples of the phenolic antioxidant include Irganox1010 (registered trademark, the same applies hereinafter) and Irganox 1076 produced by BASF CORPORATION, ADK STAB AO-50 and ADK STAB AO-60 produced by ADEKA CORPORATION, and the like.

The addition ratio of the antioxidant is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound, in the case of blending.

The antioxidant may contain only 1 kind, or may contain 2 or more kinds. When 2 or more species are contained, the total amount preferably falls within the above range.

Various additives may be added to the polycarbonate copolymer and polysiloxane compound of the present invention within the range not departing from the gist of the present invention. Examples of the additive include at least 1 additive selected from a flame retardant, a flame retardant aid, an ultraviolet absorber, a mold release agent and a colorant, and preferably at least 1 additive selected from a flame retardant and a mold release agent is contained.

Further, an antistatic agent, a fluorescent whitening agent, an antifogging agent, a flowability improver, a plasticizer, a dispersant, an antibacterial agent, and the like may be added as long as desired physical properties are not significantly impaired.

< flame retardant >

Various additives may be added to the polycarbonate copolymer and the polysiloxane compound of the present invention within a range not departing from the gist of the present invention. As the flame retardant, an organic metal salt flame retardant, a phosphorus flame retardant, an organosilicon flame retardant and the like can be blended. Examples of the flame retardant that can be used in the present invention include flame retardants (flame retardant compositions) described in paragraphs 0085 to 0093 of Japanese patent application laid-open No. 2016-183422, the contents of which are incorporated herein by reference.

< ultraviolet absorber >

Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxalanilide compounds, malonate compounds, hindered amine compounds, and phenyl salicylate compounds. Among these, benzotriazole-based or benzophenone-based organic ultraviolet absorbers are preferred. Specific examples of the benzotriazole compound include 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- [2 '-hydroxy-3', 5 '-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -benzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butyl-phenyl) -benzotriazole, 2- (2 '-hydroxy-3' -tert-butyl-5 '-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5' -di-tert-amyl) -benzotriazole, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol ], 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol, 2' - (1, 4-phenylene) bis [4H-3, 1-benzoxazin-4-one ], [ (4-methoxyphenyl) -methylene ] -propanedioic acid dimethyl ester, 2- (2H-benzotriazol-2-yl) p-cresol, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylmethyl) phenol, 2- [ 5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6- (tert-butyl) phenol, 2, 4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetrabutyl) phenol, 2' -methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetrabutyl) phenol ], [ methyl-3- [ 3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate-polyethylene glycol ] condensate and the like. Among the above, 2- (2' -hydroxy-5 ' -tert-octylphenyl) benzotriazole and 2,2' -methylene-bis [4- (1,1,3, 3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol ] are preferable. Specific examples of the benzophenone-based ultraviolet absorber include 2, 4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octyloxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy-4-octadecyloxy-benzophenone, 2' -dihydroxy-4-methoxy-benzophenone, 2' -dihydroxy-4, 4 ' -dimethoxy-benzophenone, and 2,2', 4,4 ' -tetrahydroxy-benzophenone. Specific examples of the phenyl salicylate-based ultraviolet absorber include phenyl salicylate and 4-tert-butyl-phenyl salicylate. Specific examples of the triazine-based ultraviolet absorber include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, 2- [4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl ] -5- (octyloxy) phenol, and the like. Specific examples of the hindered amine-based ultraviolet absorber include bis (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate.

The proportion of the ultraviolet absorber added is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 3 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound.

The ultraviolet absorber may be used in only 1 kind, or may be used in 2 or more kinds. When 2 or more kinds are used, the total amount is preferably in the above range.

< Release agent >

Examples of the release agent include carboxylic acid esters, polysiloxane compounds, paraffin (polyolefin) and the like. Specifically, the silicone oil composition includes at least 1 compound selected from the group consisting of an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000, and a silicone-based silicone oil. Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic mono-, di-or tricarboxylic acids. Among them, the aliphatic carboxylic acid also includes alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are C6-36 mono-or dicarboxylic acids, and more preferred are C6-36 aliphatic saturated monocarboxylic acids. Specific examples of the aliphatic carboxylic acid include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, lacceric acid, melissic acid, tetracosanoic acid, montanic acid, glutaric acid, adipic acid, and azelaic acid. As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, the same carboxylic acids as those of the above-mentioned aliphatic carboxylic acids can be used. On the other hand, as the alcohol, saturated or unsaturated mono-or polyhydric alcohols can be cited. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having not more than 30 carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols having not more than 30 carbon atoms are more preferred. Among them, the aliphatic group also includes alicyclic compounds. Specific examples of the alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2-dihydroxyperfluoropropanol, neopentyl glycol, ditrimethylolpropane, dipentaerythritol, and the like. In addition, the ester compound may contain an aliphatic carboxylic acid and/or an alcohol as impurities, or may be a mixture of a plurality of compounds. Specific examples of the ester of an aliphatic carboxylic acid and an alcohol include beeswax (a mixture containing beeswax palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerol monopalmitate, glycerol monostearate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and the like. Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and an alpha-olefin oligomer having 3 to 12 carbon atoms. Among them, the aliphatic hydrocarbon also includes alicyclic hydrocarbon. In addition, these hydrocarbon compounds may also be partially oxidized. Among these, paraffin, polyethylene wax or a partial oxide of polyethylene wax is preferable, and paraffin, polyethylene wax are more preferable. The number average molecular weight is preferably 200 to 5000. These aliphatic hydrocarbons may be a single substance or a mixture of aliphatic hydrocarbons having different constitutional components or molecular weights as long as the main component is within the above range. Examples of the silicone-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone oil. More than 2 kinds of them may be used in combination.

The addition ratio of the release agent is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound.

The release agent may be used in only 1 kind, or may be used in 2 or more kinds. When 2 or more kinds are used, the total amount is preferably in the above range.

< coloring agent >

The colorant may be any of a dye and a pigment, and examples thereof include an inorganic pigment, an organic pigment, and an organic dye. Examples of the inorganic pigment include: sulfide-based pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; oxide-based pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron-based brown, titanium-cobalt-based green, cobalt blue, copper-chromium-based black, and copper-iron-based black; chromic acid-based pigments such as yellow lead and molybdate orange; and ferrocyanide pigments such as prussian blue. Examples of the organic pigment and organic dye used as the colorant include phthalocyanine-based dyes such as copper phthalocyanine blue and copper phthalocyanine green (the dyes and pigments are referred to as "dyes and pigments", the same applies hereinafter); azo dyes such as nickel azo yellow; fused polycyclic dye pigments such as thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based pigments; quinoline-based, anthraquinone-based, heterocyclic-based, and methyl-based dyes and pigments. Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dye pigments, and the like are preferable from the viewpoint of thermal stability.

For the purpose of improving workability during extrusion and improving dispersibility in the resin composition, a master batch of a colorant with a polystyrene resin, a polycarbonate resin, or an acrylic resin may be used.

The addition ratio of the colorant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and further preferably 2 parts by mass or less, and 0.1 part by mass or more, per 100 parts by mass of the polycarbonate copolymer or the polysiloxane compound. The colorant may be used in 1 kind alone or in 2 or more kinds. When 2 or more kinds are used, the total amount is preferably in the above range.

Molded body other than lens

The shape, pattern, color, size, and the like of the molded article obtained using the polycarbonate copolymer or the polysiloxane compound are not limited, and may be arbitrarily set according to the use thereof. Specific examples of the molded article include electric and electronic devices, OA (Office Automation) devices, information terminal devices, machine parts, household electric appliances, vehicle parts, building components, various containers, leisure goods, groceries, parts of lighting equipment, and the like, parts of various household electric appliances, housings, containers, covers, storage units, cases, and covers or cases of lighting equipment. Examples of the electric and electronic devices include a display device such as a personal computer, a game machine, a television receiver, a liquid crystal display device, or a plasma display device, a printer, a copier, a scanner, a facsimile machine, an electronic organizer, or a Personal Digital Assistant (PDA), an electronic desktop computer, an electronic dictionary, a camera, a video camera, a mobile phone, a battery pack, a drive or reading device for a storage medium, a mouse, a numeric keypad, a CD (Compact Disc) player, an MD (mini Disc) player, and a portable broadcast-audio player. Further, molded articles include automobile parts (vehicle-mounted parts) such as illuminated signboards, liquid crystal backlights, illuminated displays, traffic signs, screens, reflectors, and instrument parts, toys, and ornaments.

The polycarbonate copolymer and the polysiloxane compound of the present invention have excellent impact resistance, high fluidity when melted, and can give a molded article having a fine structure, and therefore, are suitably used as an electrical/electronic component for vehicle mounting, a machine component, and a vehicle component. Examples of such members include automobile interior panels, automobile lamp lenses, automobile interior lenses, automobile lens protection covers, automobile light guide plates, and the like.

Method for forming molded body

The method for producing the molded article of the present invention is not particularly limited, and a molding method generally used for polycarbonate resin compositions can be arbitrarily used. Examples thereof include injection molding, ultrahigh-speed injection molding, injection compression molding, two-color molding, gas-assist hollow molding, molding using a heat-insulating mold, molding using a rapid-heating mold, foam molding (including supercritical fluid), in-mold injection molding, IMC (in-mold coating molding) molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, and the like. In addition, a molding method using a hot runner system can also be used.

Other resins

The polycarbonate copolymer and the polysiloxane compound of the present invention may contain a resin other than the polycarbonate copolymer and a resin other than the polysiloxane compound of the present invention as needed, unless the desired physical properties are significantly impaired. Examples of such other resins include thermoplastic polyester resins such as the polycarbonate copolymer of the present invention and polycarbonate resins other than polysiloxane compounds, polyethylene terephthalate resins (PET resins), polytrimethylene terephthalate resins (PTT resins), and polybutylene terephthalate resins (PBT resins); styrene resins such AS polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), and methyl methacrylate-styrene copolymer (MS resin); core/shell elastomers such as methyl methacrylate-acrylic rubber-styrene copolymer (MAS), and elastomers such as polyester elastomers; polyolefin resins such as cyclic cycloolefin resin (COP resin) and cyclic Cycloolefin (COP) copolymer resin; polyamide resin (PA resin); polyimide resin (PI resin); polyetherimide resins (PEI resins); a polyurethane resin (PU resin); polyphenylene ether resin (PPE resin); polyphenylene sulfide resin (PPS resin); polysulfone resin (PSU resin); polymethacrylate resin (PMMA resin); polycaprolactone, and the like.

Examples

[ examples of polycarbonate resins ]

< determination of polystyrene-reduced weight average molecular weight (Mw) >)

Calibration curves were prepared using GPC (gel permeation chromatography) and chloroform as a developing solvent, using STANDARD polystyrene (Shodex STANDARD, SM-105) of known molecular weight (molecular weight distribution ═ 1). According to the measured standard polystyrene, the dissolution time and the molecular weight value of each peak are marked, and a 3-order formula is used for approximation to prepare a correction curve.

Then, the weight average molecular weight (Mw) was determined as a polystyrene equivalent value from the following equation based on the obtained calibration curve.

[ calculation formula ]

Mw＝Σ(W_i×M_i)/Σ(W_i)

(in the above formula, i represents the i-th division point at which the molecular weight M is divided, and W_iDenotes the weight of the ith, M_iRepresents the molecular weight of the ith. Wherein the molecular weight M represents the molecular weight of the calibration curve in terms of polystyrene at the time of dissolution. )

[ measurement conditions ]

An apparatus: labsolutions manufactured by Shimadzu corporation

Column chromatography: guard column (Shodex GPC K-G4A). times.1, analytical column (Shodex GPC K-805L). times.2 this

Solvent: chloroform (HPLC grade)

Injection amount: 10 μ L

Sample concentration: 2000ppm of

Solvent flow rate: 1mL/min

Measurement temperature: 40 deg.C

The detector: RI (Ri)

< measurement of content ratio of Low molecular weight Compound having weight average molecular weight (Mw) of 1000 or less >

The proportion of low molecular weight compounds having an Mw of 1000 or less in the polycarbonate resin is calculated from the area of retention time 20.5min to 21.5 min/the area ratio of 0min to 21.5min (GPC area ratio) based on the data obtained by GPC analysis under the above conditions.

Specifically, GPC analysis was performed under the conditions described in < measurement of polystyrene-equivalent weight average molecular weight (Mw) > item, and the content ratio of the low-molecular weight compound (B/a × 100 (%)) was measured based on the ratio of the GPC area (a) of the peak having a retention time (retention time) of 21.5 minutes or less, which is considered to correspond to the total compound amount contained in the sample of the polycarbonate resin, to the GPC area (B) of the peak confirmed during 20.5 minutes to 21.5 minutes, which is considered to correspond to the retention time of the low-molecular weight compound amount having a weight average molecular weight of 1,000 or less.

< determination of glass transition temperature (Tg) >

A test piece of 5 to 12mg was accurately weighed in an AI automatic sampling sample container (RDC aluminum container, 6.8mm diameter, 2.5mm height cylinder container) as a measurement sample, and the upper part of the sample container was sealed with an AI automatic sampling lid to prepare a sample.

The measurement was carried out under a nitrogen atmosphere (nitrogen flow rate: 50ml/min) using a Differential Scanning Calorimeter (DSC), and 10.0mg of sapphire was used as a standard substance for the reference cell. Then, the measurement sample adjusted to 30 ℃ is heated to 280 ℃ at 20 ℃/min, cooled at 20 ℃/min and cooled to 30 ℃. Then, the temperature was raised to 280 ℃ at 10 ℃/min for measurement.

A measuring device: differential Scanning Calorimeter (DSC) (product name "DSC-7020", manufactured by Hitachi height New technology, Kabushiki Kaisha)

< determination of Low molecular weight Compounds (phenol (PhOH), bisphenol A (BPA), Dimethyldiphenoxysilane (DMDPS), Diphenyl carbonate (DPC) >)

10g of the sample was dissolved in 60g of methylene chloride to prepare a resin solution, and 150g of ethanol was added dropwise to the resin solution under stirring over 30 minutes. The precipitate was filtered off with a NoA5 filter paper, and the filtrate was concentrated with an evaporator to obtain an oligomer component a.

The obtained precipitate was dissolved in 60g of methylene chloride to prepare a resin solution, and 150g of ethanol was added dropwise to obtain a precipitate and an oligomer component b.

The obtained oligomer components a and b were dissolved in methylene chloride to prepare a solution of 1000. mu.g/mL, which was analyzed and quantified by GC/FID.

The quantitative value is a converted value of 2, 2-bis (4-hydroxyphenyl) propane obtained from a calibration curve of 2, 2-bis (4-hydroxyphenyl) propane prepared in advance.

[ measurement conditions of GC/FID ]

An apparatus: GC2025 manufactured by Shimadzu corporation

Column: capillary column DB-35, 30mm × 0.25mm × 0.25 μm

Temperature rise conditions: 40-300 deg.C (keeping for 5min), 10 deg.C/min

Injection port temperature: 300 ℃, injection amount: 1.0 μ L (slit ratio 1:20)

Carrier gas: he (He)

Air flow rate: 400mL/min

·H₂Flow rate: 40mL/min

Make-up gas: 30mL/min

Standard substance: 2, 2-bis (4-hydroxyphenyl) propane

< determination of Cyclic dimer >

The content of the above cyclic dimer contained in the polycarbonate copolymer was measured as follows.

A20 g sample of the polycarbonate copolymer was dissolved in 120g of methylene chloride to prepare a resin solution, and 200g of ethanol was added dropwise to the resin solution while stirring over 30 minutes. The precipitate was filtered off with a NoA5 filter paper, and the filtrate was concentrated with an evaporator to obtain an oligomer component A and a precipitate A.

Subsequently, the obtained precipitate a was dissolved in 120g of methylene chloride to prepare a resin solution, and 200g of ethanol was added dropwise to the resin solution while stirring over 30 minutes. The precipitate was filtered off with a NoA5 filter paper, and the filtrate was concentrated with an evaporator to obtain an oligomer component B and a precipitate B.

Then, the obtained precipitate B was dissolved in 120g of methylene chloride to prepare a resin solution, and 200g of ethanol was added dropwise to the resin solution while stirring. The precipitate was filtered off with a NoA5 filter paper, and the filtrate was concentrated with an evaporator to obtain an oligomer component C and a precipitate C.

The obtained oligomer components A, B and C were dissolved in methylene chloride to prepare a solution of 1000. mu.g/mL, and the cyclic dimer was analyzed by GC-Q-MS/FID. The quantitative value is a converted value of 2, 2-bis (4-hydroxyphenyl) propane obtained from a calibration curve of 2, 2-bis (4-hydroxyphenyl) propane prepared in advance.

[ measurement conditions of GC-Q-MS/FID ]

An apparatus: agilent Technologies Ltd, Agilent-7890B/Agilent-5975CMSD insert XL MSD with TAD

Column: DB-5MS, 15mm × 0.25mm × 0.1 μm

Regulator (MS): 0.18mm × 1.44mm

Regulator (FID): 0.18mm × 0.53mm

Temperature rise conditions: 50 deg.C (2 min holding) -320 deg.C (15 min holding), 20 deg.C/min

Injection port temperature: 300 deg.C

Injection amount: 1.0 μ L (slit ratio 1:10)

Carrier gas: he (He)

FID/MS ratio: 1/1

Aux temperature: 300 deg.C

Scan range: m/z 33 to 700

Scan rate: 2.22scan/s

FID temperature: 300 deg.C

·H₂Flow rate: 30mL/min

Air flow rate: 400mL/min

Supplementation: 25mL/min

Standard substance: 2, 2-bis (4-hydroxyphenyl) propane

Quantification of cyclic dimers: quantification of peak intensity from 16.6min

< fluidity (Q value) >

The melt flow volume (cm) per unit time measured at 280 ℃ under a load of 160kg^－3Sec) (Shimadzu Kabushiki Kaisha)The preparation method comprises the following steps: the melt flow volume was measured in a CFT-500D type (nozzle diameter 1mm × nozzle length 10mm), and the value per unit time was calculated from the flow length of 7.0 to 10.0 mm).

< Charpy impact test >

The Charpy impact strength (kJ/m) of the test piece obtained by molding was measured in accordance with JIS-K7111²)。

< method for measuring refractive index (nd) >

Refractive index (nd): the thickness of the 3mm rectangular plate made of the polycarbonate copolymer obtained in the examples was measured by the method according to JIS-K-7142 using an Abbe's refractometer.

Method for measuring Abbe number (vd)

For a rectangular plate having a thickness of 3mm and made of the polycarbonate resin obtained in the examples, refractive indices at 23 ℃ of 486nm, 589nm and 656nm were measured using an Abbe refractometer, and Abbe number was calculated from the following formula.

νd＝(nd－1)/(nF－nC)

nd: refractive index at wavelength of 589nm

nC: refractive index at wavelength of 656nm

nF: synthesis of Dimethyldiphenoxysilane having refractive index at wavelength of 486nm (Synthesis example 1)

Dimethyldiphenoxysilane is synthesized by the method described in reference to US 2012/184702.

At 50 ℃ and N₂176.34g (1.87mol) of phenol were stirred under an atmosphere, and 113.24g (0.88mol) of dimethyldichlorosilane was added dropwise thereto over 30 min. After 1 hour after completion of the dropwise addition, the by-product was distilled off at 170 ℃ under reduced pressure of 200 hPa. The reaction solution was cooled to room temperature, and the product was dissolved in 300mL of methylene chloride. The product dissolved in methylene chloride was washed 2 times with 300mL of a 10% NaOH solution, and the organic layer was extracted. The organic layer was washed 2 times with 300mL of water, and the washed organic layer was extracted. After residual water was removed by anhydrous magnesium sulfate, methylene chloride was distilled off by an evaporator to obtain an oily component.

The obtained oily component was analyzed by 1H-NMR and confirmed to be dimethyldiphenoxysilane (1H-NMR (CDCl3, 500MHz, δ; ppm) ═ 0.378 (s; 6H), 6.942, 6.944 (d; 4H), 6.959, 6.961, 6.995 (t; 2H), 7.230, 7.245, 7.257 (t; 4H)). The molar yield was 66%.

(example A-1)

Into a 300ml four-necked flask equipped with a stirrer were charged 104.97g (0.46mol) of 2, 2-bis (4-hydroxyphenyl) propane, 4.58g (0.02mol) of dimethyldiphenoxysilane, 101.46g (0.47mol) of diphenyl carbonate and 2.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 20 minutes.

Then, phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 20 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein the pressure is adjusted to be 27000Pa, 24000Pa, 20000Pa, 17000Pa, 14000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 200Pa or less in a stepwise manner from atmospheric pressure at the time of pressure reduction.

Mw of the silicone-containing polycarbonate copolymer was measured by GPC, and the result was 44373.

The Tg of the above copolymer was measured by DSC to find that it was 136 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, 1% weight loss was 411 ℃.

(example A-2)

Into a 300ml four-necked flask equipped with a stirrer were charged 72.85g (0.32mol) of 2, 2-bis (4-hydroxyphenyl) propane, 7.9g (0.032mol) of dimethyldiphenoxysilane, 65.86g (0.31mol) of diphenyl carbonate and 0.6. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1.5 hours to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction was maintained for 1.5 hours, whereby a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure was obtained. During the pressure reduction, the pressure is adjusted to be 27000Pa and 24000Pa, 20000Pa, 16000Pa, 8000Pa, 4000Pa, 2000Pa, 400Pa, or less in a stepwise manner from the atmospheric pressure.

Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 48035.

The Tg of the above copolymer was measured by DSC to give 129 ℃.

The Q value of the copolymer was measured, and found to be 75 (. times.10)^－2cm³/sec)。

(example A-3)

Into a 100ml four-necked flask equipped with a stirrer were charged 21.69g (0.10mol) of 2, 2-bis (4-hydroxyphenyl) propane, 9.52g (0.39mol) of dimethyldiphenoxysilane, 13.5g (0.63mol) of diphenyl carbonate and 7.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction was maintained for 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Further, during the pressure reduction, the pressure is adjusted to be 27000Pa and 24000Pa, 20000Pa, 16000Pa, 8000Pa, 4000Pa, 2000Pa, 400Pa, or less stepwise from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured using GPC and found to be 54007.

The Tg of the above copolymer was measured by DSC to find that it was 101 ℃.

The Q value of the copolymer was measured, and found to be 114 (. times.10)^－2cm³/sec)。

(example A-4)

30.69g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 25.46g (0.10mol) of dimethyldiphenoxysilane, 9.96g (0.046mol) of diphenyl carbonate and 7.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction was maintained for 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the pressure reduction, the pressure is adjusted to be 27000Pa and 24000Pa, 20000Pa, 16000Pa, 8000Pa, 4000Pa, 2000Pa, 400Pa, or less in a stepwise manner from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 63068.

The Tg of the above copolymer was measured by DSC to find that it was 75 ℃.

(example A-5)

Into a 100ml four-necked flask equipped with a stirrer were charged 30.63g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 31.05g (0.13mol) of dimethyldiphenoxysilane, 5.04g (0.024mol) of diphenyl carbonate and 7.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction was maintained for 2 hours to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the pressure reduction, the pressure is adjusted to be 27000Pa and 24000Pa, 20000Pa, 16000Pa, 8000Pa, 4000Pa, 2000Pa, 400Pa, or less in a stepwise manner from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was determined by GPC and found to be 49161.

The Tg of the above copolymer was measured by DSC to give 62 ℃.

Examples A-6 to A-14

Copolymers were produced in the same manner as in example a-1, except that the raw material compounds were changed as shown in table 1 below. The properties of the obtained copolymer are shown in table 1.

[ Table 1]

(examples A to 15)

2, 2-bis (4-hydroxyphenyl) propane 2310g (10.13mol), dimethyldiphenoxysilane 1849.26g (7.58mol), diphenyl carbonate 753.04g (3.52mol) and cesium carbonate 14.0. mu. mol/mol as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 10-liter reactor equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 40 minutes.

Then, phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 1 hour and 15 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. During the pressure reduction, the pressure was adjusted so as to be changed stepwise from atmospheric pressure to 27000Pa, 24000Pa, 20000Pa, 17000Pa, 14000Pa, 12000Pa, 8000Pa, 4000Pa, or 100Pa or less.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 208939.

The Tg of the above copolymer was measured by DSC to find that it was 74.2 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 337.1 ℃.

(examples A to 16)

2497g (10.95mol) of 2, 2-bis (4-hydroxyphenyl) propane, 1997.20g (8.19mol) of dimethyldiphenoxysilane, 813.00g (3.80mol) of diphenyl carbonate and 3.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged into a 10-liter reactor equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 45 minutes.

Then, phenol distilled off from the reaction system was removed by condensation using a cooling tube for 2 hours and 30 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein the pressure is adjusted to be 27000Pa, 24000Pa, 20000Pa, 17000Pa, 14000Pa, 10000Pa, 6000Pa, 4000Pa, or 100Pa or less in a stepwise manner from the atmospheric pressure at the time of pressure reduction.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 81885.

The Tg of the above copolymer was measured by DSC to find that it was 75.1 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 380.6 ℃.

The amount of low molecular weight compounds contained in the copolymer was determined by GC, and as a result, the copolymer contained 415ppm of PhOH, 475ppm of BPA, 122ppm of DMDPS, and 44ppm of DPC.

(reference example)

19.99g of the copolymer obtained in example A-16 was dissolved in 121.22g of methylene chloride and 196g of ethanol was added dropwise to the stirred resin solution over 30 minutes in accordance with the method for measuring a cyclic dimer described above. The precipitate was filtered off with a NoA5 filter paper, and the filtrate was concentrated with an evaporator to obtain 0.652g of an oligomer component A. The precipitate was again dissolved in methylene chloride, ethanol was added dropwise, and the operation of separating the precipitate from the oligomer component was repeated 2 times (0.268 g as oligomer component B, 0.177g as oligomer component C, and 18.99g as copolymer reprecipitate, i.e., precipitate). The obtained oligomer components A, B and C were dissolved in methylene chloride to obtain a 1000. mu.g/mL liquid, and the amount of cyclic dimer in the reprecipitated copolymer was 0.71 wt% as a result of analysis by GC-Q-MS/FID.

In addition, the Q value of the silicone-containing polycarbonate copolymer obtained in examples A-16 was 117 (. times.10)^－2cm³Sec) in reference exampleThe Q value of the obtained reprecipitated product of the silicone-containing polycarbonate copolymer was 74 (. times.10)^－2cm³Sec). It is found that the inclusion of the cyclic dimer increases the Q value and the fluidity.

[ Table 2]

(example A-17)

In a 100ml four-necked flask equipped with a stirrer were charged 30.99g (0.07mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 13.01g (0.05mol) of diphenyldimethoxysilane, 5.28g (0.02mol) of diphenyl carbonate, and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 30 minutes.

Then, phenol and methanol distilled out of the reaction system were condensed and removed by a cooling tube for 1 hour and 10 minutes to conduct an ester exchange reaction, and the inside of the system was brought to 260 ℃ and the reduced pressure was brought to 2hPa or less, and the reaction was maintained for 15 minutes, whereby a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure was obtained. Wherein the pressure is adjusted to be lower than 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, and 200Pa stepwise from the atmospheric pressure at the time of pressure reduction.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 115683.

The Tg of the above copolymer was measured by DSC and found to be 110.9 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 351.4 ℃.

(examples A to 18)

Into a 100ml four-necked flask equipped with a stirrer were charged 24.71g (0.071mol) of 9, 9-bis (4-hydroxyphenyl) fluorene, 18.00g (0.074mol) of diphenyldimethoxysilane, 0.831g (0.004mol) of diphenyl carbonate, and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 9, 9-bis (4-hydroxyphenyl) fluorene) to replace the inside of the system with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 15 minutes.

Then, phenol and methanol distilled out of the reaction system were condensed and removed by a cooling tube for 1 hour and 20 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a transparent polycarbonate copolymer having an arylenesiloxane structure, which was yellowed. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 80000Pa, 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, and 200Pa stepwise from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 12992.

The Tg of the above copolymer was measured by DSC to find that it was 165.5 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 361.1 ℃.

(examples A to 19)

17.07g (0.04mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 12.06g (0.03mol) of 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 12.99g (0.05mol) of diphenyldimethoxysilane, 5.26g (0.02mol) of diphenyl carbonate and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to the sum of the moles of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene and 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol and methanol distilled out of the reaction system were condensed and removed by a cooling tube for 1 hour and 20 minutes to conduct an ester exchange reaction, the inside of the system was brought to 260 ℃ and the reduced pressure was brought to 2hPa or less, and the system was kept for 1 hour and 20 minutes to obtain a transparent polycarbonate copolymer having an arylenesiloxane structure, which was browned. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 80000Pa, 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, and 200Pa stepwise from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 23272.

The Tg of the above copolymer was measured by DSC to find that it was 140.4 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 349.4 ℃.

(examples A to 20)

Into a 100ml four-necked flask equipped with a stirrer were charged 24.71g (0.071mol) of 9, 9-bis (4-hydroxyphenyl) fluorene, 1.80g (0.007mol) of dimethyldiphenoxysilane, 16.21g (0.066mol) of diphenyldimethoxysilane, 0.83g (0.004mol) of diphenyl carbonate, and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was relative to the number of moles of 9, 9-bis (4-hydroxyphenyl) fluorene), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 210 ℃ and stirred for 25 minutes.

Thereafter, phenol and methanol distilled out of the reaction system were condensed and removed by a cooling tube for 1 hour and 25 minutes to conduct an ester exchange reaction, and the inside of the system was brought to 260 ℃ and the reduced pressure was brought to 2hPa or less, and the reaction was maintained for 1 hour, whereby a transparent polycarbonate copolymer having an arylenesiloxane structure, which was yellowed, was obtained. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 80000Pa, 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, and 200Pa stepwise from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 28050.

The Tg of the copolymer was measured by DSC to obtain a value of 171.4 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, the 1% weight loss was 339.1 ℃.

(example A-21)

In a 100ml four-necked flask equipped with a stirrer were charged 10.22g (0.07mol) of isosorbide, 17.60g (0.07mol) of diphenyldimethoxysilane and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to that of isosorbide), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 100 ℃ and stirred for 10 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour 55 minutes to conduct an ester exchange reaction, the inside of the system was brought to 200 ℃ and the reduced pressure was brought to 2hPa or less, and the reaction was maintained for 1 hour 30 minutes to obtain a transparent arylene siloxane having yellowing. Wherein, when the pressure is reduced, the pressure is adjusted to be 90000Pa, 80000Pa, 70000Pa, 60000Pa, 50000Pa, 30000Pa, 10000Pa, 6000Pa, 2000Pa, and 200Pa or less in a stepwise manner from the atmospheric pressure.

Mw of the arylenesiloxane was determined by GPC and found to be 9125.

The Tg of the above copolymer was measured by DSC to find that it was 71.1 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and as a result, 1% weight loss was 256.2 ℃.

(example A-22)

In a 100ml four-necked flask equipped with a stirrer were charged 17.50g (0.07mol) of bis (4-hydroxyphenyl) sulfone, 17.42g (0.07mol) of diphenyldimethoxysilane and 30.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was relative to the relative mole of bis (4-hydroxyphenyl) sulfone), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 25 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 15 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a transparent arylene siloxane which was slightly reddened. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 80000Pa, 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, and 200Pa stepwise from the atmospheric pressure.

Mw of the arylene siloxane was measured using GPC and found to be 12806.

The Tg of the arylene siloxane was measured by DSC and found to be 123.6 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and as a result, 1% weight loss was 384.7 ℃.

(example A-23)

Into a 100ml four-necked flask equipped with a stirrer were charged 31.00g (0.07mol) of 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, 18.98g (0.08mol) of diphenyldimethoxysilane, and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative number of moles with respect to 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 30 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 10 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a colorless and transparent arylene siloxane. Wherein the pressure is adjusted to be lower than 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 3000Pa, 2000Pa, 1000Pa, and 200Pa stepwise from the atmospheric pressure at the time of pressure reduction.

Mw of the arylenesiloxane was measured by GPC, and the result was 46225.

The Tg of the arylene siloxane was measured by DSC and found to be 97.4 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and the 1% weight loss was 350.6 ℃.

(examples A to 24)

Into a 100ml four-necked flask equipped with a stirrer were charged 24.71g (0.07mol) of 9, 9-bis (4-hydroxyphenyl) fluorene, 18.95g (0.08mol) of diphenyldimethoxysilane, and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 9, 9-bis (4-hydroxyphenyl) fluorene), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 15 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a transparent arylene siloxane having yellowing. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 80000Pa, 60000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 3000Pa, 2000Pa, and 200Pa stepwise from the atmospheric pressure.

Mw of the arylene siloxane was measured using GPC, and the result was 27028.

The Tg of the arylene siloxane was measured by DSC to find that it was 169.7 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and the 1% weight loss was 364.8 ℃.

(example A-25)

In a 100ml four-necked flask equipped with a stirrer were charged 15.26g (0.07mol) of bis (4-hydroxyphenyl) sulfide, 17.42g (0.07mol) of diphenyldimethoxysilane and 30.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was relative to the relative mole of bis (4-hydroxyphenyl) sulfide), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 190 ℃ and stirred for 15 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 2 hours and 15 minutes to conduct an ester exchange reaction, the inside of the system was brought to 260 ℃ and the reduced pressure was brought to 2hPa or less, and the reaction was maintained for 1 hour and 20 minutes to obtain a colorless and transparent arylene siloxane. Wherein, when the pressure is reduced, the pressure is adjusted to be 90000Pa, 80000Pa, 70000Pa, 60000Pa, 50000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, and 200Pa or less in a stepwise manner from the atmospheric pressure.

Mw of the arylenesiloxane was measured by GPC, and the result was 56797.

The Tg of the arylene siloxane was measured by DSC to be 73.2 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and as a result, 1% weight loss was 391.6 ℃.

The results of examples A-15 to 25 and the reference example are shown in Table 3.

[ Table 3]

(examples A to 26)

Into a 100ml four-necked flask equipped with a stirrer were charged 37.73g (0.07mol) of 9, 9-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene, 19.47g (0.07mol) of dimethyldiphenoxysilane, and 30.0. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the amount of the catalyst was the relative mole number to 9, 9-bis (6-hydroxynaphthyl) fluorene), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 210 ℃ and stirred for 30 minutes.

Then, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction, the temperature in the system was brought to 280 ℃ and the reduced pressure was brought to 2hPa or less, and the reaction was maintained for 1 hour and 50 minutes to obtain a transparent arylene siloxane having yellowing. Wherein, when the pressure is reduced, the pressure is adjusted to be lower than 30000Pa, 27500Pa, 25000Pa, 22500Pa, 20000Pa, 17500Pa, 15000Pa, 12500Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa and 200Pa stepwise from the atmospheric pressure.

Mw of the arylenesiloxane was measured by GPC, and the result was 39353.

The Tg of the arylene siloxane was measured by DSC and found to be 138 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA and found to be 369.3 ℃ at 1%.

(example A-27)

In a 200ml four-necked flask equipped with a stirrer were charged 61.04g (0.33mol) of 4,4 '-dihydroxy-biphenyl, 89.64g (0.37mol) of dimethyldiphenoxysilane, and 3.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 4, 4' -dihydroxy-biphenyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 60 minutes.

Then, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 2 hours to obtain a colorless and transparent arylene siloxane. Wherein the pressure is adjusted to be 27000Pa, 24000Pa, 20000Pa, 17000Pa, 14000Pa, 10000Pa, 6000Pa, 4000Pa, or 100Pa or less in a stepwise manner from the atmospheric pressure at the time of pressure reduction.

Mw of the arylene siloxane was measured using GPC, and found to be 46000.

The Tg of the above arylene siloxane was measured by DSC to be 70.4 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA and was found to be 378 ℃ at 1%.

(examples A to 28)

In a 200ml four-necked flask equipped with a stirrer were charged 79.71g (0.43mol) of 4,4 '-dihydroxy-biphenyl, 107.42g (0.44mol) of diphenyldimethoxysilane and 3.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 4, 4' -dihydroxy-biphenyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 30 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube over 2 hours to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 2 hours to obtain a colorless and transparent arylene siloxane. Wherein, when the pressure is reduced, the pressure is adjusted to be 90000Pa, 80000Pa, 70000Pa, 60000Pa, 50000Pa, 40000Pa, 20000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, and 200Pa or less in a stepwise manner from the atmospheric pressure.

Mw of the arylenesiloxane was measured by GPC, and found 17000.

The Tg of the above arylene siloxane was measured by DSC and found to be 110 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA and was found to be 345 ℃ at 1%.

(example A-29)

In a 300ml four-necked flask equipped with a stirrer were charged 39.06g (0.21mol) of 4,4 '-dihydroxy-biphenyl, 38.58g (0.16mol) of dimethyldiphenoxysilane, 15.60g (0.07mol) of diphenyl carbonate and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 4, 4' -dihydroxy-biphenyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 20 minutes.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 10 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein, when the pressure is reduced, the pressure is adjusted to be changed from the atmospheric pressure to 30000Pa, 25000Pa, 20000Pa, 15000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 100Pa or less in a stepwise manner.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC, and the result was 33710.

The Tg of the above copolymer was measured by DSC to find that it was 78.8 ℃. The weight loss of the above copolymer was measured using TG-DTA, and the 1% weight loss was 357 ℃.

(example A-30)

In a 300ml four-necked flask equipped with a stirrer were charged 39.06g (0.21mol) of 4,4 '-dihydroxy-biphenyl, 35.00g (0.14mol) of diphenyldimethoxysilane, 15.60g (0.07mol) of diphenyl carbonate and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 4, 4' -dihydroxy-biphenyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 20 minutes.

Then, methanol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 1hPa or less, and the reaction was maintained for 10 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein, when the pressure is reduced, the pressure is adjusted to be changed from the atmospheric pressure to 30000Pa, 25000Pa, 20000Pa, 15000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 100Pa or less in a stepwise manner.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 11845.

The Tg of the above copolymer was measured by DSC to give a value of 120 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, 1% weight loss was 363 ℃.

(example A-31)

In a 100ml four-necked flask equipped with a stirrer were charged 26.18g (0.07mol) of 2,2 '-bishydroxyethoxy-1, 1' -binaphthyl, 19.82g (0.08mol) of dimethyldiphenoxysilane, and 30. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the amount of the catalyst was the relative mole number to 2,2 '-bishydroxyethoxy-1, 1' -binaphthyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 210 ℃ and stirred for 35 minutes.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a colorless and transparent arylene siloxane. Wherein, during the pressure reduction, the pressure is adjusted to be changed from the atmospheric pressure to 27500Pa, 25000Pa, 22500Pa, 20000Pa, 17500Pa, 15000Pa, 12500Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 100Pa or less in a stepwise manner.

Mw of the arylenesiloxane was measured using GPC, and the result was 19975.

The Tg of the above arylene siloxane was measured by DSC and found to be 54 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and as a result, 1% weight loss was 296 ℃.

(examples A-32)

In a 100ml four-necked flask equipped with a stirrer were charged 26.18g (0.07mol) of 2,2 '-bishydroxyethoxy-1, 1' -binaphthyl, 5.40g (0.03mol) of diphenyl carbonate, 12.65g (0.05mol) of dimethyldiphenoxysilane and 30. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the amount of the catalyst was the relative mole number to 2,2 '-bishydroxyethoxy-1, 1' -binaphthyl), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 220 ℃ and stirred for 1 hour.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 10 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 1hPa or less, and the reaction was maintained for 1 hour and 20 minutes to obtain a colorless and transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein, during the pressure reduction, the pressure is adjusted to be changed from the atmospheric pressure to 27500Pa, 25000Pa, 22500Pa, 20000Pa, 17500Pa, 15000Pa, 12500Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 100Pa or less in a stepwise manner.

The Mw of the silicone-containing polycarbonate copolymer was determined by GPC and was 32178.

The Tg of the above copolymer was measured by DSC to find that it was 74 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, 1% weight loss was 317 ℃.

(example A-33)

In a 100ml four-necked flask equipped with a stirrer were charged 10.22g (0.07mol) of isosorbide, 5.20g (0.02mol) of diphenyl carbonate, 12.86g (0.05mol) of dimethyldiphenoxysilane and 15.0. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to that of isosorbide), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 200 ℃ and stirred for 30 minutes.

Thereafter, phenol distilled out of the reaction system was condensed and removed by a cooling tube for 1 hour and 20 minutes to conduct an ester exchange reaction, the temperature in the system was made 260 ℃ and the reduced pressure was made 2hPa or less, and the reaction was maintained for 1 hour and 30 minutes to obtain a yellowing-free transparent polycarbonate copolymer having an arylenesiloxane structure. Wherein, when the pressure is reduced, the pressure is adjusted to be changed from the atmospheric pressure to 30000Pa, 25000Pa, 20000Pa, 15000Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa, 200Pa or less in a stepwise manner.

The Mw of the silicone-containing polycarbonate copolymer was determined using GPC and was 39378.

The Tg of the above copolymer was measured by DSC to obtain 55 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, 1% weight loss was 242 ℃.

(examples A to 34)

In a 100ml four-necked flask equipped with a stirrer were charged 21.28g (0.07mol) of 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 19.82g (0.08mol) of dimethyldiphenoxysilane and 30.0. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the amount of the catalyst was the relative mole number to 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 210 ℃ and stirred for 30 minutes.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 50 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 2hPa or less, and the reaction was maintained for 1 hour to obtain a colorless and transparent arylene siloxane. During the pressure reduction, the pressure is adjusted to be lower than 30000Pa, 25000Pa, 20000Pa, 17500Pa, 15000Pa, 12500Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa and 200Pa in a stepwise manner from the atmospheric pressure.

Mw of the arylene siloxane was measured using GPC, and found to be 15708.

The Tg of the above arylene siloxane was measured by DSC and found to be 51 ℃. The weight loss of the above arylene siloxane was measured using TG-DTA, and as a result, 1% weight loss was 236 ℃.

(examples A to 35)

In a 100ml four-necked flask equipped with a stirrer were charged 21.28g (0.07mol) of 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 5.20g (0.02mol) of diphenyl carbonate, 12.86g (0.05mol) of dimethyldiphenoxysilane and 30.0. mu. mol/mol of sodium hydrogencarbonate as a catalyst (the amount of the catalyst was relative to the relative mole number of 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 210 ℃ and stirred for 30 minutes.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube for 1 hour and 30 minutes to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 2hPa or less, and the reaction was maintained for 1 hour to obtain a transparent polycarbonate copolymer having an arylenesiloxane structure. During the pressure reduction, the pressure is adjusted to be lower than 30000Pa, 25000Pa, 20000Pa, 17500Pa, 15000Pa, 12500Pa, 10000Pa, 8000Pa, 6000Pa, 4000Pa, 2000Pa, 1000Pa and 200Pa in a stepwise manner from the atmospheric pressure.

The Mw of the silicone-containing polycarbonate copolymer was measured by GPC and found to be 68693.

The Tg of the above copolymer was measured by DSC to give 63 ℃. The weight loss of the above copolymer was measured using TG-DTA, and as a result, 1% weight loss was 252 ℃.

Comparative example A-1

Into a 100ml four-necked flask equipped with a stirrer were charged 17.51g (0.08mmol) of 2, 2-bis (4-hydroxyphenyl) propane, 20.93g (0.09mol) of dimethyldiphenoxysilane and 7. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, phenol distilled off from the reaction system was condensed and removed by a cooling tube for 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction system was maintained for 2 hours to obtain a colorless and transparent polyarylene siloxane.

Mw of the polyarylene siloxane was measured by GPC, and the result was 63257.

The Tg of the above copolymer was measured by DSC to obtain 54 ℃.

Comparative example A-2

Mw of polycarbonate (Ilpilon S-3000, Mitsubishi gas chemical) was measured by GPC, and the result was 51252.

The Tg of the polycarbonate was measured by DSC to find that the temperature was 149 ℃.

Comparative example A-3

The diol compound used was Iupizeta EP6000 manufactured by mitsubishi gas chemical corporation, that is, BPEF: 9, 9-bis [4- (2-hydroxyethoxy) phenyl]A fluorene polycarbonate resin was used as comparative example A-3. The polycarbonate resin of comparative example A-3 had Mw of 30000 and Q value of 97X 10^－2cm³(sec), Tg of 142 ℃, refractive index (nd) of 1.638 and Abbe number (vd) of 23.5.

It was confirmed that examples A-17, 19 and 23 using the same diol compound had improved fluidity (the Q value could be significantly improved) without significantly changing the optical properties, as compared with comparative example A-3.

The results of examples A-26 to A-35 and comparative examples A-1 and 2 are shown in Table 4.

[ Table 4]

(examples A to 36)

10g of the polycarbonate copolymer obtained in example A-3 and a polycarbonate (manufactured by Mitsubishi gas chemical Co., Ltd., Ifpil) were mixed together using a kneading extruder (LABO PLASTOMILL4C150, manufactured by Toyo Seiki Seisaku-Sho Ltd.)on S-3000)190g was kneaded and extruded at 280 ℃. The Q value of the obtained composition was 11.9 (. times.10)^－2cm³Sec). Further, the composition was dried at 110 ℃ for 12 hours by a dryer, and then a Charpy impact test piece was formed at a resin temperature of 300 ℃ and a mold temperature of 90 ℃ by an injection molding machine (SHINKO SELLBIC CO., manufactured by LTD. "C-Mobile"), and a notched Charpy impact test was carried out in accordance with JIS-K7111, and as a result, 60.9kJ/m²。

(example A-37)

10g of the polycarbonate copolymer obtained in example A-4 and 190g of a polycarbonate (Ifpilon S-3000, manufactured by Mitsubishi gas chemical) were kneaded and extruded at 280 ℃ using a kneading extruder (LABO PLASTOMILL4C150, manufactured by Toyo Seiki Seisaku-Sho Ltd.). The Q value of the obtained composition was 14.1 (. times.10)^－2cm³Sec). Further, the composition was dried at 110 ℃ for 12 hours by a dryer, and then a Charpy impact test piece was formed at a resin temperature of 300 ℃ and a mold temperature of 90 ℃ by an injection molding machine (SHINKO SELLBIC CO., manufactured by LTD. "C-Mobile"), and a notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 65.8kJ/m²。

(example A-38)

A polycarbonate copolymer 150g obtained in example A-16 and a polycarbonate (Ipiplon E-2000, manufactured by Mitsubishi gas chemical corporation) 1850g were kneaded at a resin temperature of 280 ℃ by a kneading extrusion injection molding machine (Sodick TR100EH high-speed injection molding machine), and then injection-molded at a mold temperature of 80 ℃ and a pressure of 90MPa to form a Charpy impact test piece. The notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 70.1kJ/m². Further, the Q value of the obtained composition was 5.5 (. times.10)^－2cm³/sec)。

(example A-39)

300g of the polycarbonate copolymer obtained in example A-16 and 1700g of a polycarbonate (Iipilon E-2000, manufactured by Mitsubishi gas chemical corporation) were kneaded at a resin temperature of 280 ℃ using a kneading extrusion injection molding machine (Sodick TR100EH high-speed injection molding machine), and then injection-molded at a mold temperature of 80 ℃ under a pressure of 90MPa,a Charpy impact test piece was formed. The notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 76.7kJ/m². Further, the Q value of the obtained composition was 8.1 (. times.10)^－2cm³/sec)。

(example A-40)

600g of the polycarbonate copolymer obtained in example A-16 and 1400g of a polycarbonate (Ipiplon E-2000, manufactured by Mitsubishi gas chemical corporation) were kneaded at a resin temperature of 280 ℃ by using a kneading extrusion injection molding machine (Sodick TR100EH high-speed injection molding machine), and then injection-molded at a mold temperature of 80 ℃ and a pressure of 90MPa to form a test piece for Charpy impact test. The notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 6.9kJ/m². Further, the Q value of the obtained composition was 17.2 (. times.10)^－2cm³/sec)。

Comparative example A-4

The Q value of polycarbonate (Ifpilon S-3000, product of Mitsubishi gas chemical) was 8.0 (. times.10)^－2cm³Sec). After the polycarbonate was dried at 110 ℃ for 12 hours by a dryer, a Charpy impact test piece was formed at a resin temperature of 300 ℃ and a mold temperature of 90 ℃ by an injection molding machine ("C-Mobile" manufactured by LTD.) and a notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 62.9kJ/m²。

Comparative example A-5

2000g of polycarbonate (Ifpilon E-2000, product of Mitsubishi gas chemical) was kneaded at a resin temperature of 300 ℃ using a kneading extrusion injection molding machine (Sodick TR100EH), and then injection-molded at a mold temperature of 80 ℃ and a pressure of 90MPa to form a test piece for Charpy impact test. The notched Charpy impact test was carried out in accordance with JIS-K7111, and the result was 72.7kJ/m². Further, the Q value of the obtained composition was 2.8 (. times.10)^－2cm³/sec)。

The results of examples A-36 to 40 and comparative examples A-4 and 5 are shown in Table 5 below.

[ Table 5]

[ examples of Silicone Compounds ]

Examples of the polysiloxane compound are described below.

< polystyrene equivalent weight average molecular weight (Mw) >)

A calibration curve was prepared using GPC (gel permeation chromatography) using chloroform as a developing solvent and standard polystyrene of a known molecular weight (molecular weight distribution ═ 1). Calculated from the retention time of GPC based on this calibration curve.

< glass transition temperature (Tg) >

Measured using a Differential Scanning Calorimeter (DSC). In the obtained DSC curve, the intersection point between a straight line extending from the base line on the low temperature side to the high temperature side and a tangent line drawn at the point where the gradient of the curve in the stepwise change portion of the glass transition becomes maximum is obtained.

(Synthesis example 2) Synthesis of Dimethyldiphenoxysilane

7.5g (20.2mmol, molar amount of Si: 101.0mmol), 21.6g (101.0mmol) of diphenyl carbonate and 33mg (0.1mmol) of cesium carbonate as a catalyst were stirred at 200 ℃ for 60 minutes under a nitrogen atmosphere instead.

Subsequently, the reaction mixture was cooled to 40 ℃ and then distilled under reduced pressure at 150 ℃ under reduced pressure of 4hPa to give 23.7g of a colorless oily component.

By using¹The oily component obtained was analyzed by H-NMR to confirm that it was dimethyldiphenoxysilane. (¹H-NMR(CDCl₃500MHz, δ; ppm) 0.378 (s; 6H) 6.942, 6.944 (d; 4H) 6.959, 6.961, 6.995 (t; 2H) 7.230, 7.245, 7.257 (t; 4H) ) molar yield was 96.0%.

(example B-1)

30.03g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 33.50g (0.14mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Thereafter, the phenol distilled off from the reaction system was removed by condensation through a cooling tube for 1.5 hours to effect transesterification reaction, the temperature in the system was made 240 ℃ and the reduced pressure was made 4hPa or less, and the reaction system was maintained for 1.5 hours to obtain a colorless and transparent polyarylene siloxane.

Mw of the polyarylene siloxane was measured by GPC, and the result was 26699.

(example B-2)

30.03g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 34.40g (0.14mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 33521.

(example B-3)

30.05g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 34.69g (0.14mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 30603.

(example B-4)

30.03g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 35.10g (0.14mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 36940.

(example B-5)

30.08g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 36.00g (0.15mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst is the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 39994.

The Tg of the polyarylene siloxane was measured by DSC, which was 49 ℃.

(example B-6)

30.03g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 37.38g (0.15mol) of dimethyldiphenoxysilane and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane) were charged in a 100ml four-necked flask equipped with a stirrer, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 34196.

(example B-7)

Into a 100ml four-necked flask equipped with a stirrer were charged 17.51g (0.077mol) of 2, 2-bis (4-hydroxyphenyl) propane, 20.93g (0.086mol) of dimethyldiphenoxysilane and 7. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Thereafter, the phenol distilled off from the reaction system was condensed and removed by a cooling tube over 1 hour to conduct an ester exchange reaction so that the temperature in the system became 260 ℃ and the reduced pressure became 4hPa or less, and the reaction system was maintained for 1.5 hours to obtain a colorless and transparent polyarylene siloxane.

Mw of the polyarylene siloxane was measured by GPC, and the result was 63257.

The Tg of the polyarylene siloxane was measured by DSC, which was 54 ℃.

(Synthesis example 3)

14.9g (0.19mol) of octaphenylcyclotetrasiloxane of the following formula (3), 16.1g (0.08mol) of diphenyl carbonate and 33mg (0.1mmol) of cesium carbonate as a catalyst were stirred at 200 ℃ for 10 minutes while replacing with nitrogen. After cooling to room temperature, 20g of heptane was added to the solidified reaction mixture, and hot filtration was carried out after it was brought to 90 ℃. The obtained filtrate was left at room temperature for 3 days, whereby white crystals were precipitated. 10g of heptane cooled to 5 ℃ was further added, and crystals on the obtained filter paper were collected by filtration of the mixture and dried at 40 ℃ under reduced pressure of 1hPa for 45 hours to obtain 24.1g of a white powder. By using¹H-NMRThe powder thus obtained was analyzed, and it was confirmed to be diphenyldiphenoxysilane. Diphenyldiphenoxysilane (C)¹H-NMR (CDCl3, 500MHz, delta; ppm) 6.915, 6.927, 6.939, 6.952, 6.965 (p; 6H), 7.142, 7.155, 7.169 (t; 4H), 7.354, 7.366, 7.379 (t; 4H), 7.425, 7.437, 7.449 (t; 2H)), 7.750, 7.762 (d; 4H) in that respect The molar yield was 81.1%.

(example B-8)

In a 100ml four-necked flask equipped with a stirrer were charged 11.75g (0.052mol) of 2, 2-bis (4-hydroxyphenyl) propane, 20.25g (0.055mol) of diphenyldiphenoxysilane and 20. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Mw of the polyarylene siloxane was measured by GPC, and the result was 24482.

The Tg of the polyarylene siloxane was measured by DSC, which was 89 ℃.

Comparative example B-1

In a 100ml four-necked flask equipped with a stirrer, 20.00g (0.088mol) of 2, 2-bis (4-hydroxyphenyl) propane and 23.62g (0.097mol) of dimethyldiphenoxysilane were charged, and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, the system was brought to 240 ℃ and the reduced pressure was brought to 4hPa (400Pa) or less, and an ester exchange reaction was attempted, but the raw materials were distilled off and the reaction did not proceed.

Comparative example B-2

Into a 100ml four-necked flask equipped with a stirrer were charged 21.28g (0.093mol) of 2, 2-bis (4-hydroxyphenyl) propane, 25.12g (0.10mol) of dimethyldiphenoxysilane, and 11. mu. mol/mol of cesium carbonate as a catalyst (the amount of the catalyst was the relative mole number to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Thereafter, the temperature of the system was raised to 240 ℃ over 1.5 hours under normal pressure, and the temperature was maintained for another 1.5 hours, whereby a colorless transparent polyarylene siloxane was obtained.

Mw of the polyarylene siloxane was measured by GPC, and the result was 1547.

Comparative example B-3

Into a 100ml four-necked flask equipped with a stirrer were charged 29.96g (0.13mol) of 2, 2-bis (4-hydroxyphenyl) propane, 36.10g (0.15mol) of dimethyldiphenoxysilane and 16600. mu. mol/mol of cesium carbonate as a catalyst (or 16.6mmol/mol, the amount of the catalyst being the relative mole number with respect to 2, 2-bis (4-hydroxyphenyl) propane), and the inside of the system was replaced with a nitrogen atmosphere. The raw materials were melted by heating at 180 ℃ and stirred for 30 minutes.

Then, the phenol distilled off from the reaction system was removed by condensation using a cooling tube over 1 hour to conduct an ester exchange reaction so that the temperature in the system became 240 ℃ and the reduced pressure became 4hPa or less, and the reaction system was maintained for 1.5 hours to obtain a colorless and transparent polyarylene siloxane.

Mw of the colorless and transparent polyarylene siloxane was measured by GPC, and the result was 886.

Comparative example B-4

A100 ml four-necked flask equipped with a stirrer was charged with 30.75g (0.14mol) of 2, 2-bis (4-hydroxyphenyl) propane and 36.90g (0.15mol) of dimethyldiphenoxysilane.

Immediately thereafter, the system was brought to 240 ℃ and the reduced pressure was brought to 4hPa (400Pa) or less, and an ester exchange reaction was attempted, but the raw materials were distilled off and the reaction did not proceed.

The results of the examples and comparative examples are shown in table 6 below.

[ Table 6]

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