Copolycarbonates and polycarbonate compositions containing the same
阅读说明：本技术 共聚碳酸酯和包含该共聚碳酸酯的聚碳酸酯组合物 (Copolycarbonates and polycarbonate compositions containing the same ) 是由 黄英荣 孙永旭 黄大铉 洪武镐 于 2020-07-29 设计创作，主要内容包括：本公开涉及一种共聚碳酸酯和包含该共聚碳酸酯的聚碳酸酯组合物。所述共聚碳酸酯具有优异的抗冲击性,特别是低温抗冲击性和优异的耐候性。因此,使用所述共聚碳酸酯,预期提供即使在极端环境下性能也不改变的汽车外部材料。(The present disclosure relates to a copolycarbonate and polycarbonate compositions comprising the same. The copolycarbonates have excellent impact resistance, particularly low temperature impact resistance, and excellent weatherability. Therefore, with the copolycarbonate, it is expected to provide an automobile exterior material whose performance does not change even under extreme environments.)
1. A copolycarbonate comprising: a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the first and second,
R1to R4Each independently is hydrogen, C1-10Alkyl radical, C1-10An alkoxy group, or a halogen,
z is C which is unsubstituted or substituted by phenyl1-10Alkylene, unsubstituted or substituted by C1-10Alkyl substituted C3-15Cycloalkylene, O, S, SO2Or a combination of carbon and oxygen, or CO,
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R5、R6、R7、R8and R9Each independently is hydrogen; halogen; an allyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-15An alkyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-10An alkoxy group; or unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An aryl group, a heteroaryl group,
R10is hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
each X is independently C1-10Alkylene, - (OCO) - (C)1-10Alkylene) -, or- (COO) - (C)1-10Alkylene) -,
y is each independently hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
l is C3-10An alkylene group or a substituted alkylene group,
Ar1、Ar2and Ar3Each independently is unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An arylene group, a cyclic or cyclic alkylene group,
n and m are each independently an integer from 1 to 999 and l is an integer from 0 to 999.
2. The copolycarbonate according to claim 1, wherein the repeating unit represented by chemical formula 2 is represented by the following chemical formula 2-1:
[ chemical formula 2-1]
In the chemical formula 2-1, the,
R5、R6、R7、R8and R9Each independently is hydrogen; halogen; an allyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-15An alkyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-10An alkoxy group; or unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An aryl group, a heteroaryl group,
R10is hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
each X is independently C1-10Alkylene, - (OCO) - (C)1-10Alkylene) -, or- (COO) - (C)1-10Alkylene) -,
y is each independently hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
l is C3-10An alkylene group or a substituted alkylene group,
n and m are each independently an integer from 1 to 999 and l is an integer from 0 to 999.
3. The copolycarbonate according to claim 1, wherein the repeating unit represented by chemical formula 2 is represented by the following chemical formula 2-2:
[ chemical formula 2-2]
In the chemical formula 2-1, the,
n and m are each independently an integer from 1 to 999 and l is an integer from 0 to 999.
4. The copolycarbonate according to claim 1, wherein the content of the repeating unit represented by chemical formula 2 is 5 to 20 wt% based on the total weight of the repeating units represented by chemical formulae 1 and 2.
5. A polycarbonate composition comprising the copolycarbonate of claim 1.
6. The polycarbonate composition of claim 5, further comprising a polycarbonate that does not comprise a repeating unit represented by chemical formula 2.
Technical Field
[ Cross-reference to related applications ]
The present application claims the rights of korean patent application No. 10-2019-.
The present disclosure relates to a copolycarbonate and polycarbonate compositions comprising the same.
Background
Polycarbonates are prepared by polycondensation of aromatic diols such as bisphenol a with carbonate precursors such as phosgene, have excellent impact strength, dimensional stability, heat resistance, transparency, and the like, and are used in various fields such as exterior materials for electric and electronic products, automobile parts, building materials, optical elements, clothing materials, and the like.
Recently, for such polycarbonates, a great deal of research is being attempted to copolymerize two or more aromatic diol compounds having different structures to introduce repeating units of different structures into the main chain of the polycarbonate, thereby obtaining desired properties for application in more diverse fields.
Polycarbonate is also used as an automobile exterior material due to its excellent impact resistance, but recently, customer demand for a new material exhibiting not only excellent impact resistance as polycarbonate but also excellent scratch resistance, weather resistance, and the like has increased.
Disclosure of Invention
Technical problem
An object of the present disclosure is to provide a copolycarbonate having not only excellent impact resistance but also significantly improved weather resistance, and a polycarbonate composition comprising the same.
Technical scheme
According to one embodiment of the present disclosure, there is provided a copolycarbonate comprising: a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the first and second,
R1to R4Each independently is hydrogen, C1-10Alkyl radical, C1-10An alkoxy group, or a halogen,
z is C which is unsubstituted or substituted by phenyl1-10Alkylene, unsubstituted or substituted by C1-10Alkyl substituted C3-15Cycloalkylene, O, S, SO2Or a combination of CO and at least one of CO,
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R5、R6、R7、R8and R9Each independently is hydrogen; halogen; an allyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-15An alkyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-10An alkoxy group; or unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An aryl group, a heteroaryl group,
R10is hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
each X is independently C1-10Alkylene, - (OCO) - (C)1-10Alkylene) -, or- (COO) - (C)1-10Alkylene) -,
y is each independently hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20Aryl, L is C3-10An alkylene group or a substituted alkylene group,
Ar1、Ar2and Ar3Each independently is unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An arylene group, a cyclic or cyclic alkylene group,
n and m are each independently an integer from 1 to 999 and l is an integer from 0 to 999.
In accordance with another embodiment of the present disclosure, a polycarbonate composition comprising the copolycarbonate is provided.
Advantageous effects
The copolycarbonate according to one embodiment has excellent impact resistance, particularly low-temperature impact resistance, and excellent weather resistance. Therefore, with the copolycarbonate, it is expected to provide an automobile exterior material whose performance does not change even under extreme environments.
Detailed Description
Hereinafter, a copolycarbonate according to a specific embodiment of the present disclosure and a polycarbonate composition comprising the same will be described in detail.
According to an embodiment of the present disclosure, there is provided a copolycarbonate comprising a repeating unit represented by the following chemical formula 1 and a repeating unit represented by the following chemical formula 2:
[ chemical formula 1]
In the chemical formula 1, the first and second,
R1to R4Each independently is hydrogen, C1-10Alkyl radical, C1-10An alkoxy group, or a halogen,
z is C which is unsubstituted or substituted by phenyl1-10Alkylene, unsubstituted or substituted by C1-10Alkyl substituted C3-15Cycloalkylene, O, S, SO2Or a combination of CO and at least one of CO,
[ chemical formula 2]
In the chemical formula 2, the first and second organic solvents,
R5、R6、R7、R8and R9Each independently is hydrogen; halogen; an allyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-15An alkyl group; unsubstituted or selected from halogen, C1-10Alkoxy and C6-20C substituted by one or more of aryl groups1-10An alkoxy group; or unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An aryl group, a heteroaryl group,
R10is hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
each X is independently C1-10Alkylene, - (OCO) - (C)1-10Alkylene) -, or- (COO) - (C)1-10Alkylene) -,
y is each independently hydrogen, C1-6Alkyl, halogen, hydroxy, C1-6Alkoxy, or C6-20An aryl group, a heteroaryl group,
l is C3-10An alkylene group or a substituted alkylene group,
Ar1、Ar2and Ar3Each independently is unsubstituted or selected from halogen, C1-15Alkyl and C1-10C substituted by one or more of alkoxy6-20An arylene group, a cyclic or cyclic alkylene group,
n and m are each independently an integer from 1 to 999 and l is an integer from 0 to 999.
The copolycarbonate refers to a polymer in which a polysiloxane structure is introduced on a main chain of a polycarbonate, an aromatic group connected by an ester group is introduced on a side chain of the polysiloxane structure or a repeating unit including two or more aromatic groups connected by an ester group is introduced, and specifically, a repeating unit represented by chemical formula 1 and a repeating unit represented by chemical formula 2 are included.
The main chain of the copolycarbonate is a repeating unit formed by a reaction of a diol compound and a carbonate precursor, and includes a repeating unit represented by chemical formula 1.
In chemical formula 1, R1To R4Each independently is, for example, hydrogen, methyl, methoxy, chlorine or bromine.
In chemical formula 1, Z may be a linear or branched C unsubstituted or substituted with a phenyl group1-10An alkylene group. Specifically, Z may be, for example, methylene, ethane-1, 1-diyl, propane-2, 2-diyl, butane-2, 2-diyl, 1-phenylethane-1, 1-diyl, or diphenylmethylene. Further, in chemical formula 1, Z may be, for example, cyclohexane-1, 1-diyl, O, S, SO2Or CO.
The repeating unit represented by chemical formula 1 may be derived from a group selected from bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3-bromophenyl) propane, 2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4, 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, and one or more aromatic diol compounds selected from 1, 1-bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) diphenylmethane.
The phrase "derived from the aromatic diol compound" means that the hydroxyl group of the aromatic diol compound reacts with the carbonate precursor to form a repeating unit represented by chemical formula 1. For example, in the case of polymerizing an aromatic diol compound bisphenol a with a carbonate precursor triphosgene, the repeating unit represented by chemical formula 1 is represented by the following chemical formula 1-1.
[ chemical formula 1-1]
As the carbonate precursor, one or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate may be used. Preferably, triphosgene or phosgene can be used.
The main chain of the copolycarbonate includes, as a repeating unit represented by chemical formula 2, a polysiloxane structure in which an aromatic group connected by an ester group or a repeating unit including two or more aromatic groups connected by an ester group is introduced on a side chain thereof, in addition to the repeating unit represented by chemical formula 1.
By introducing a polysiloxane structure in the main chain, the copolycarbonate can exhibit excellent impact resistance, particularly low-temperature impact resistance, and excellent chemical resistance. Further, by introducing an aromatic group linked by an ester group or introducing a repeating unit comprising two or more aromatic groups linked by an ester group on a side chain of a polysiloxane structure, it is possible to exhibit remarkably improved weather resistance while maintaining excellent impact resistance.
The repeating unit represented by chemical formula 2 may be formed by reacting a modified polyorganosiloxane represented by the following chemical formula 3, which includes a polysiloxane structure, on a side chain of which an aromatic group connected by an ester group is introduced or a repeating unit including two or more aromatic groups connected by an ester group is introduced, wherein hydroxyl groups are bonded at both ends, with a carbonate precursor.
[ chemical formula 3]
In chemical formula 3, R5To R10、X、Y、L、Ar1To Ar3M, n and l are as defined in chemical formula 2.
The modified polyorganosiloxane represented by chemical formula 3 may be prepared by the following method: for example, a polysiloxane structure in which an aromatic group connected by an ester group or a repeating unit containing two or more aromatic groups connected by an ester group is introduced is prepared as a repeating unit repeating n times, then a side chain unmodified polysiloxane structure is added to the polysiloxane structure in which an aromatic group connected by an ester group or a repeating unit containing two or more aromatic groups connected by an ester group is introduced as a repeating unit repeating m times, and a terminal group containing a hydroxyphenyl group is added to the prepared polysiloxane structure.
For the preparation of the modified polyorganosiloxane, a metal catalyst may be used. As the metal catalyst, a Pt catalyst can be used, and as the Pt catalyst, a catalyst selected from the group consisting of an Ashby catalyst, a Karstedt catalyst, a Lamoreaux catalyst, a Speier catalyst, and PtCl can be used2(COD)、PtCl2(benzonitrile)2And H2PtBr6One or more of (a).
In chemical formula 2, R5、R6、R7、R8And R9May each independently be hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2, 2-trifluoroethyl, 3,3, 3-trifluoropropyl, phenyl, or naphthyl. More specifically, R5、R6、R7、R8And R9May each independently be C1-10Alkyl radical, C1-6Alkyl radical, C1-3Alkyl, or methyl.
In chemical formula 2, R10Can be hydrogen, methyl, ethyl, propyl, fluoro, chloro, bromo, iodo, hydroxy, methoxy, ethoxy, propoxy, or phenyl. More specifically, R10May be hydrogen or hydroxyl.
In chemical formula 2, X may each independently be C2-10Alkylene, - (OCO) - (C)2-10Alkylene) -, or- (COO) - (C)2-10Alkylene) -. Specifically, X may be C2-5Alkylene, - (OCO) - (C)2-5Alkylene) -, or- (COO) - (C)2-5Alkylene) -, more specifically, X may be propane-1, 3-diyl.
In chemical formula 2, Y may each independently be hydrogen or methoxy.
In chemical formula 2, L may be C3-5An alkylene group. More specifically, L may be propane-1, 3-diyl.
In chemical formula 2, Ar1、Ar2And Ar3May each independently be a benzenediyl group, a methylbenzediyl group, a methoxybenzenediyl group, a dimethylbenzenediyl group, a dimethoxybenzenediyl group, a naphthalenediyl group, a methylnaphthalenediyl group, a methoxynaphthalenediyl group, a dimethylnaphthalenediyl group, or a dimethoxynaphthalenediyl group. More specifically, Ar1、Ar2And Ar3May each independently be benzene-1, 2-diyl, benzene-1, 3-diyl or benzene-1, 4-diyl.
As an example, the repeating unit represented by chemical formula 2 may be represented by chemical formula 2-1 below.
[ chemical formula 2-1]
In chemical formula 2-1, R5To R10X, Y, L, m, n and L are as defined in chemical formula 2.
As another example, the repeating unit represented by chemical formula 2 may be represented by chemical formula 2-2 below.
[ chemical formula 2-2]
In the chemical formula 2-2, the,
m, n and l are as defined in chemical formula 2.
In chemical formula 2, chemical formula 2-1, and chemical formula 2-2, m and n represent only the ratio of the repeating unit repeated m times to the repeating unit repeated n times, and the repeating unit repeated m times and the repeating unit repeated n times may be randomly arranged.
n and m may each independently be an integer of 1 to 999 or an integer of 1 to 200. Specifically, n may be an integer of 10 or more, 15 or more, 20 or more, or 25 or more, and 100 or less, 50 or less, 45 or less, 40 or less, 35 or less, or 30 or less, and m may be an integer of 2 or more, 3 or more, 5 or more, or 7 or more, and 100 or less, 50 or less, 25 or less, 15 or less, or 10 or less.
In chemical formula 2, chemical formula 2-1, and chemical formula 2-2, l may be an integer of 0 to 200, 0 to 100,0 to 50, 0 to 20, or 0 to 10.
In the copolycarbonate, the content of the repeating unit represented by chemical formula 2 may be 1 to 99 wt%, 1 to 80 wt%, 1 to 70 wt%, 1 to 60 wt%, 1 to 50 wt%, 1 to 40 wt%, 1 to 30 wt%, 1 to 20 wt%, 3 to 20 wt%, or 5 to 20 wt%, based on the total weight of the repeating units represented by chemical formula 1 and chemical formula 2.
The copolycarbonate may be prepared by polymerizing a composition comprising an aromatic diol compound, a carbonate precursor, and a modified polyorganosiloxane represented by chemical formula 3. The aromatic diol compound, the carbonate precursor, and the modified polyorganosiloxane represented by chemical formula 3 are as described above.
In the polymerization process, the aromatic diol compound and the modified polyorganosiloxane represented by chemical formula 3 may be used at appropriate contents according to the contents of the repeating units represented by chemical formula 1 and chemical formula 2 to be introduced into the copolycarbonate. In addition, the carbonate precursor may be used in a substantially equal number of moles to the aromatic diol compound and the modified polyorganosiloxane group represented by chemical formula 3.
Preferably, the polymerization is performed by interfacial polymerization, and during the interfacial polymerization, the polymerization reaction can be performed at atmospheric pressure and low temperature, and the molecular weight is easily controlled. Further, the interfacial polymerization may include a step of performing prepolymerization, introducing a coupling agent, and then performing polymerization again, and in this case, a high molecular weight copolycarbonate may be obtained.
Preferably, the polymerization temperature is 0 ℃ to 40 ℃ and the reaction time is 10 minutes to 5 hours. Further, it is preferable to maintain the pH above 9 or above 11 during the reaction.
The solvent that can be used in the polymerization is not particularly limited as long as it is used in the art for the polymerization of copolycarbonate, and for example, halogenated hydrocarbons such as dichloromethane, chlorobenzene, and the like can be used.
In addition, preferably, the polymerization is carried out in the presence of an acid binder, and as the acid binder, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like, or an amine compound such as pyridine or the like can be used.
In addition, it is preferable that the polymerization is carried out in the presence of a molecular weight controlling agent in order to control the molecular weight of the copolycarbonate. As the molecular weight controlling agent, C can be used1-20Specific examples of the alkylphenol include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. The molecular weight controlling agent may be introduced before, during, or after initiation of polymerization. The content of the molecular weight controlling agent may be 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or more and 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound, and within these ranges, a desired molecular weight may be obtained.
In addition, in order to promote the polymerization reaction, a reaction promoter such as: tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, etc.; a quaternary ammonium compound; quaternary phosphonium compounds, and the like.
The weight average molecular weight (g/mol) of the copolycarbonate may preferably be 1,000 to 100,000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight may be 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 27,000 or more, or 28,000 or more. The weight average molecular weight may be 34,000 or less, 33,000 or less, or 32,000 or less.
Meanwhile, according to another embodiment of the present disclosure, there is provided a polycarbonate composition comprising the copolycarbonate.
The copolycarbonate has been described in detail above, and detailed description is omitted.
The polycarbonate composition may comprise one or more, two or more, or three or more of the above copolycarbonates.
In addition, the polycarbonate composition may further include a polycarbonate that does not include the repeating unit represented by chemical formula 2.
Specifically, as the polycarbonate not containing the repeating unit represented by chemical formula 2, for example, there may be mentioned: a polycarbonate comprising one or more repeating units represented by chemical formula 1; or a polycarbonate comprising one or more repeating units represented by chemical formula 1 and a repeating unit represented by the following chemical formula 4, in chemical formula 4, no aromatic group connected by an ester group or no repeating unit comprising two or more aromatic groups connected to an ester group is introduced in a side chain of chemical formula 2; and the like.
[ chemical formula 4]
In the chemical formula 4, the first and second organic solvents,
R5'、R6'、R7'、R8'、R9', X ', Y ', m ' and n ' are respectively R of chemical formula 25、R6、R7、R8、R9X, Y, m and n, R11Such as R7' as defined.
The polycarbonate composition may further comprise various additives known in the art.
The polycarbonate composition has excellent low-temperature impact resistance and weather resistance, among others. Therefore, with the composition, it is expected that an automobile exterior material whose performance does not change even under extreme environments can be provided.
Hereinafter, the action and effect of the present invention will be described in detail by specific examples. However, these embodiments are presented only as examples of the present invention, and the scope of the claims of the present invention is not limited thereto.
Preparation example 1: preparation of modified polyorganosiloxanes
Into a 1L flask, 9.62g (40.0mmol) of tetramethylcyclotetrasiloxane was introduced, 0.005g (25ppm) of Karstedt's platinum catalyst was introduced, and reacted at 90 ℃ for 1 hour, and then, 1.49g (11.1mmol) of 2-allylphenol was added, and reacted for 3 hours. At room temperature, 200mL of dichloromethane solvent was introduced, and 1.36g of benzoic acid was added dropwise. Thereafter, 1.41g of oxalyl chloride and 0.01g of DMF were added dropwise and reacted at room temperature for about 4 hours, and the solvent was removed by a rotary vacuum evaporator.
38.56g (130.0mmol) of octamethylcyclotetrasiloxane and 2.44g (18.2mmol) of tetramethyldisiloxane were added to the modified polyorganosiloxane, and then, the mixture was introduced into a 1-L flask together with 1 part by weight of an acidic clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 ℃ for 4 hours. After the reaction was complete, it was diluted with ethyl acetate and rapidly filtered using celite.
To the resulting terminal-unmodified polyorganosiloxane was added 0.01g (50ppm) of Karstedt's platinum catalyst and reacted at 90 ℃ for 1 hour, and then, 4.93g (36.8mmol) of 2-allylphenol was additionally added and reacted for 3 hours. After the reaction was complete, unreacted siloxane was removed by evaporation at 120 ℃ at 1 torr. The structure of the modified polyorganosiloxane thus prepared is as follows1H NMR identifies the repeating units n and m as 26 and 8, respectively, and l as 0.
Preparation example 2: preparation of modified polyorganosiloxanes
Into a 1L flask, 9.62g (40.0mmol) of tetramethylcyclotetrasiloxane was introduced, 0.005g (25ppm) of Karstedt's platinum catalyst was introduced, and reacted at 90 ℃ for 1 hour, and then, 1.49g (11.1mmol) of 2-allylphenol was added, and reacted for 3 hours. And, at room temperature, 200mL of a dichloromethane solvent was introduced, and 4.60g of 3-hydroxybenzoic acid was added dropwise. Thereafter, 4.07g of oxalyl chloride and 0.01g of DMF were added dropwise and stirred at room temperature for about 4 hours, and 1.36g of benzoic acid and 1.41g of oxalyl chloride were additionally added and stirred at room temperature for about 4 hours further to complete the reaction, and the solvent was removed by a rotary vacuum evaporator.
38.56g (130.0mmol) of octamethylcyclotetrasiloxane and 2.44g (18.2mmol) of tetramethyldisiloxane were added to the modified polyorganosiloxane, and then, the mixture was introduced into a 1-L flask together with 1 part by weight of an acidic clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 ℃ for 4 hours. After the reaction was complete, it was diluted with ethyl acetate and rapidly filtered using celite.
To the resulting terminal-unmodified polyorganosiloxane was added 0.01g (50ppm) of Karstedt platinum catalyst and reacted at 90 ℃ for 1 hour, and then, 4.93g (36.8mmol) of 2-allylphenol was additionally added and reacted for 3 hours. After the reaction was complete, unreacted siloxane was removed by evaporation at 120 ℃ at 1 torr. The structure of the modified polyorganosiloxane thus prepared is as follows1H NMR confirmed that, in the repeating units, n and m were 26 and 8, respectively, and l was 3.
Preparation example 3: preparation of modified polyorganosiloxanes
50.43g (170.0mmol) of tetramethylcyclotetrasiloxane, 38.56g (130.0mmol) of octamethylcyclotetrasiloxane and 2.44g (18.2mmol) of tetramethyldisiloxane were mixed, and then, the mixture was introduced into a 1-L flask together with 1 part by weight of an acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane and reacted at 60 ℃ for 4 hours. After the reaction was complete, it was diluted with ethyl acetate and rapidly filtered using celite.
To the resulting terminal-unmodified polyorganosiloxane was added 0.01g (50ppm) of Karstedt platinum catalyst and reacted at 90 ℃ for 1 hour, and then, 4.93g (36.8mmol) of 2-allylphenol was additionally added and reacted for 3 hours. After the reaction was complete, unreacted siloxane was removed by evaporation at 120 ℃ at 1 torr. The structure of the modified polyorganosiloxane thus prepared is as follows1H NMR confirmed that, among them, the number of repeating units derived from siloxane was 34.
Example 1: preparation of copolycarbonates
1784g of water, 385g of NaOH and 232g of BPA (bisphenol A) are introduced into the polymerization reactor, mixed and dissolved under a nitrogen atmosphere. To this were added 4.3g of PTBP (p-tert-butylphenol) and 26.3g of the modified polyorganosiloxane prepared in preparation example 1 dissolved in MC (dichloromethane). Then, 130g of TPG (triphosgene) was dissolved in MC, introduced and reacted for 1 hour while maintaining pH at 11 or more using NaOH aqueous solution, and after 10 minutes, 2.18g of TEA (triethylamine) was introduced to perform coupling reaction. After 1 hour 20 minutes total reaction time, the pH was lowered to 4 or less using 35 wt% aqueous HCl to remove TEA, and the reaction product was washed 3 times with distilled water to adjust the pH of the prepared polymer to 6 to 7. The resulting polymer was reprecipitated in a mixed solution of methanol and hexane, and then dried at 120 ℃ to obtain the final copolycarbonate. It was confirmed that the resulting copolycarbonate contained the repeating unit from the modified polyorganosiloxane prepared in preparation example 1 as the repeating unit represented by chemical formula 2, the content thereof was 10% by weight based on the entire repeating units, and the weight average molecular weight measured by GPC using a PC standard was 29,800 g/mol.
Example 2: preparation of copolycarbonates
A copolycarbonate was prepared by the same method as in example 1, except that the modified polyorganosiloxane prepared in preparation example 2 was used instead of the modified polyorganosiloxane prepared in preparation example 1. The copolycarbonate contained the repeating unit derived from the modified polyorganosiloxane prepared in preparation example 2 as the repeating unit represented by chemical formula 2 in an amount of about 10% by weight based on the entire repeating units.
Example 3: preparation of copolycarbonates
A copolycarbonate was prepared by the same method as in example 1, except that the content of the modified polyorganosiloxane prepared in preparation example 1 was changed to 13.16g instead of 26.30g in example 1. The copolycarbonate contained the repeating unit derived from the modified polyorganosiloxane prepared in preparation example 1 as the repeating unit represented by chemical formula 2 in an amount of about 5 wt% based on the entire repeating units.
Example 4: preparation of copolycarbonates
A copolycarbonate was prepared by the same method as in example 2, except that the content of the modified polyorganosiloxane prepared in preparation example 2 was changed to 13.16g instead of 26.30g in example 2. The copolycarbonate contained the repeating unit derived from the modified polyorganosiloxane prepared in preparation example 2 as the repeating unit represented by chemical formula 2 in an amount of about 5 wt% based on the entire repeating units.
Example 5: preparation of polycarbonate compositions
The copolycarbonate prepared in example 1 and the polycarbonate prepared in comparative example 1 below were mixed in a weight ratio of 50:50, and pelletized using a vented twin-screw extruder to prepare a polycarbonate composition.
Example 6: preparation of polycarbonate compositions
The copolycarbonate prepared in example 2 and the polycarbonate prepared in comparative example 1 below were mixed in a weight ratio of 50:50, and pelletized using a vented twin-screw extruder to prepare a polycarbonate composition.
Comparative example 1: preparation of polycarbonates
A polycarbonate was produced by the same method as in example 1, except that the modified polyorganosiloxane of production example 1 was not used.
Comparative example 2: preparation of polycarbonates
Polycarbonate was produced by the same method as example 1, except that the modified polyorganosiloxane prepared in production example 3 was used instead of the modified polyorganosiloxane prepared in production example 1.
Experimental example: evaluation of Properties of (Co) polycarbonate
The properties of the (co) polycarbonates prepared in examples and comparative examples were evaluated, and the results are shown in Table 1 below.
< preparation of test sample >
To 1 part by weight of each of the (co) polycarbonates or polycarbonate compositions prepared in examples and comparative examples, 0.050 parts by weight of tris (2, 4-di-t-butylphenyl) phosphite, 0.010 parts by weight of octadecyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and 0.030 parts by weight of pentaerythritol tetrastearate were added, and the reaction mixture was pelletized using a vented 19mm twin-screw extruder, and then, injection-molded using a HAAKE Minijet injection-molding machine at a cylinder temperature of 300 ℃ and a mold temperature of 90 ℃ to prepare test samples.
1) Weight average molecular weight (Mw): measured by GPC using Agilent 1200 series, using PC standards.
2) Melt Index (MI): measured according to ASTM D1238 (at 300 ℃ C., 1.2 kg).
3) Light transmittance: the light transmittance was measured in the range of about 350nm to 1050nm using UltraScan PRO (manufactured by HunterLab) according to ASTM D1003.
4) Yellow Index (YI): YI value at room temperature (20 ℃) was measured according to ASTM D1925 using UltraScan PRO (manufactured by HunterLab).
5) Room temperature and low temperature impact strength: room temperature and low temperature impact strength was measured at 23 ℃ and-30 ℃ according to ASTM D256(1/8 inches, notched Izod), respectively.
6) Weather resistance: l, a and b values were measured using UltraScan PRO (Hunterlab) for test specimens having a thickness of 1/8 inches. Thereafter, Weather-(Ci5000) the test specimen was left for 2250 hours, and then L, a and b values were measured by the same method and substituted in the following formula 1 to calculate Δ E.
[ formula 1]
[ Table 1]
Referring to table 1, it can be confirmed that examples 1 to 6 using copolycarbonates comprising repeating units represented by chemical formulas 1 and 2 exhibited excellent impact resistance, particularly low-temperature impact resistance, and remarkably improved weather resistance, as compared to comparative example 1, while maintaining the excellent properties of the polycarbonate of comparative example 1.
In contrast, it can be confirmed that comparative example 2 using a copolycarbonate not containing the repeating unit represented by chemical formula 2 cannot exhibit the same low-temperature impact resistance and weather resistance as the examples.
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