阅读说明：本技术 聚(亚苯基醚)共聚物方法和组合物 (Poly- (phenylene ether) copolymer method and composition ) 是由 埃伊莱姆·塔尔金-塔斯 胡塞因·塔斯 马克·R·丹尼斯顿 于 2018-03-27 设计创作，主要内容包括：在存在分子氧、包含金属离子和至少一种胺配体的聚合催化剂以及由至少95重量百分比的C<Sub>1</Sub>-C<Sub>3</Sub>醇所组成的溶剂的情况下,通过2-甲基-6-苯基苯酚和二元酚的聚合制备具有1,000至10,000克/摩尔的绝对数均分子量的2-甲基-6-苯基苯酚和二元酚的聚(亚苯基醚)共聚物,所述C<Sub>1</Sub>-C<Sub>3</Sub>醇选自甲醇、乙醇、1-丙醇和2-丙醇。聚(亚苯基醚)共聚物可以是例如2-甲基-6-苯基苯酚、2,2-双(3,5-二甲基-4-羟基苯酚)丙烷和任选地2,6-二甲苯酚的共聚物。聚(亚苯基醚)共聚物在可固化组合物、固化的组合物和制品中获得应用。(There are molecular oxygen, the polymerization catalyst comprising metal ion and at least one amine ligand and the C by least 95 weight percent 1 ‑C 3 In the case where solvent composed by alcohol, have 1 by the polymerization preparation of 2- methyl -6- phenylphenol and dihydric phenol, 2- methyl -6- the phenylphenol of 000 to 10,000 gram/mol of absolute number average molecular and poly- (phenylene ether) copolymer of dihydric phenol, the C 1 ‑C 3 Alcohol is selected from methanol, ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol.Poly- (phenylene ether) copolymer can be the copolymer of such as 2- methyl -6- phenylphenol, 2,2- bis- (3,5- dimethyl -4- hydroxyl phenol) propane and optionally 2,6- dimethlbenzene.Poly- (phenylene ether) copolymer is applied in curable compositions, cured composition and product.)

1. the method that one kind is used to form poly- (phenylene ether) copolymer, which comprises

There are molecular oxygen, polymerization catalyst and solvent comprising metal ion and at least one amine ligand in the case where, will Monohydric phenol comprising 2- methyl -6- phenylphenol and dihydric phenol reaction are to form 2- methyl -6- phenylphenol and the dihydric phenol Copolymer；

Wherein the copolymer has 1,000 to 10,000 grams/mol of absolute number average molecular；And

Wherein the solvent includes the C of at least 95 weight percent of the total weight based on the solvent₁-C₃Alcohol, the C₁-C₃Alcohol Selected from the group being made of methanol, ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol.

2. according to the method described in claim 1, wherein the polymerization catalyst includes copper ion, bromide ion and N, bis--uncle of N'- Butyl ethylenediamine.

3. method according to claim 1 or 2, wherein the total weight based on monohydric phenol and dihydric phenol, the monohydric phenol packet There is the monohydric phenol of identical substituent group containing 2- and 6- in phenol ring less than 0.5 weight percent.

4. method according to any one of claim 1-3, wherein the copolymer has 1,000 to 5,000 gram/mol Absolute number average molecular.

5. method according to claim 1 to 4, wherein the copolymer includes 80 to 99 weight percent The repetitive unit derived from the dihydric phenol of repetitive unit and 1 to 20 weight percent derived from the monohydric phenol.

6. the method according to any one of claims 1 to 5, wherein the dihydric phenol has with flowering structure:

The R wherein occurred every time¹And R²And R³And R⁴It is hydrogen, halogen, unsubstituted or take independently selected from the group being made of following item The C in generation₁-C₁₂Alkyl, condition are that the alkyl is not tertiary hydrocarbon base, C₁-C₁₂Alkylthio, C₁-C₁₂Alkyl oxygroup and C₂-C₁₂It is halogenated Alkyl oxygroup, wherein at least two carbon atom separate halogen and oxygen atom；Z is 0 or 1；And Y is selected from and is made of following item Group

The R wherein occurred every time⁵-R⁸It independently is hydrogen, C₁-C₁₂Alkyl or C₁-C₆Alkylene, wherein the R occurred twice⁵Jointly Form C₄-C₁₂Alkylidene.

7. according to the method described in claim 6, wherein z is 1.

8. method according to any one of claim 1 to 7, wherein the dihydric phenol includes bis- (3, the 5- dimethyl-of 2,2- 4- hydroxyl phenol) propane.

9. method according to any one of claim 1 to 8, wherein the amine ligand includes two (C₁-C₆Alkyl) amine；And And wherein the copolymer of 2- methyl -6- phenylphenol and the dihydric phenol includes being less than for the weight based on the copolymer Two (C of 0.005 weight percent₁-C₆Alkyl) amino.

10. method according to any one of claim 1 to 9, wherein the solvent includes at least 99 weight percent Methanol.

11. method according to any one of claim 1 to 10, in which:

The dihydric phenol includes bis- (3,5- dimethyl -4- hydroxyl phenol) propane of 2,2-；

At least one amine ligand includes two (normal-butyl) amine；

The solvent includes the methanol of at least 99 weight percent；And

The copolymer of 2- methyl -6- phenylphenol and the dihydric phenol includes the weight based on the copolymer less than 0.005 Two (normal-butyl) amino of weight percent.

12. a kind of poly- (phenylene ether) copolymer derived from the monohydric phenol comprising 2- methyl -6- phenylphenol and dihydric phenol, Described in copolymer there is 1,000 to 10,000 grams/mol of absolute number average molecular.

13. poly- (phenylene ether) copolymer according to claim 12, wherein the monohydric phenol include based on monohydric phenol and 2- and 6- in phenol ring less than 0.5 weight percent of the total weight of dihydric phenol have the monohydric phenol of identical substituent group.

14. poly- (phenylene ether) copolymer according to claim 12, wherein the copolymer has 1,000 to 5,000 Gram/mol absolute number average molecular.

15. (phenylene ether) copolymer poly- described in any one of 2 to 14 according to claim 1, wherein the copolymer includes The repetitive units derived from the monohydric phenol of 80 to 99 weight percent and 1 to 20 weight percent are derived from the binary The repetitive unit of phenol.

16. a kind of poly- (phenylene ether) copolymer having following structure:

Wherein:

R independently is methyl or two (normal-butyl) aminomethyls at each occurrence；Condition is that the copolymer fifty-fifty includes base In two (normal-butyl) aminomethyls less than or equal to 0.005 weight percent of the weight of the copolymer；And

At each occurrence independently 0 to 50, condition is x and y and is 4 to 53 x and y.

17. poly- (phenylene ether) copolymer according to claim 16, wherein x and y's and be 8 to 20.

18. a kind of curable compositions are copolymerized comprising thermosetting resin and poly- (phenylene ether) according to claim 12 Object.

19. it is a kind of by by curable compositions according to claim 18 with the time and temperature for being enough to be cured into Row heats cured composition obtained.

20. a kind of product comprising the cured composition described in claim 19.

Background technique

Poly- (phenylene ether) is with excellent waterproofness, dimensional stability and intrinsic anti-flammability and in broadband and temperature model Have in enclosing and protrudes dielectric property and famous a kind of thermoplastic.It can be by by poly- (phenylene ether) and a variety of other modelings Material, which is blended, carrys out accommodation property, such as ductility, hardness, chemical resistance and heat resistance to meet multiple terminal use, for example, fluid Engineering component, electric appliance casing, automobile component and the needs for electric wire and cable insulation.In addition, poly- (phenylene ether) with It is used in the thermoset composition of electronic application, wherein they provide improved flexibility and Jie together with other benefits Electrical property.

The use of poly- (phenylene ether) in thermoset composition has shown that a variety of tradeoffs.High-molecular-weight poly (phenylene Ether) excellent flexibility and dielectric property can be provided, but their use is related with processing difficulties, is included in thermosetting property work The high viscosity of limited dissolution and acquired solution in Conventional solvents used in industry.Low molecular weight poly- (phenylene ether) display The solubility and low solution viscosity improved out, but exist in synthesis and separation relative to high-molecular-weight poly (phenylene ether) tired It is difficult.

Synthesis by poly- (phenylene ether) of the oxidation coupling of monohydric phenol is known for a long time.See, e.g., License within 28th within 2 months within 1967 U.S. Patent No. 3,306,874 of Hay.In a kind of synthetic method, unitary is dissolved existing Oxidation coupling is carried out in the case where the solvent of phenol monomer, polymerization catalyst and product poly- (phenylene ether).This synthetic method is also It needs to remove polymerization catalyst from reaction product solution, is after this usually to be sunk by mixing its solution with non-solvent Shallow lake product is poly- (phenylene ether).In brief, this synthetic method needs a) to react, b) removing of catalyst and c) polymer Separation.The synthesis of low molecular weight poly- (phenylene ether) can be carried out in a similar way.Can by adjusting following factor, including The concentration of catalyst concn, polymerization time and dihydric phenol comonomer (if present) controls the molecular weight of polymer.

In substitution synthetic method, it is dissolved with monohydric phenol monomer and polymerization catalyst existing, but there is no the poly- (Asias of product Phenyl ether) solvent in the case where carry out oxidation coupling.In this approach, it can be formed by adjusting including solvent blend Because usually control product poly- (phenylene ether) molecular weight.For example, licensing within 28th within 2 months within 1967 the U.S. Patent No. of Hay No. 3,306,875 embodiments 27 show 2,6- dimethlbenzene in the 13:7 volume/volume mixture of benzene and normal heptane Oxidation polymerization, to obtain poly- (phenylene ether) of 0.49 deciliter/gram of intrinsic viscosity.As another example, license to U.S. Patent No. 4,463,164 of Dalton et al. are described in the solvent for monomer and catalyst and for poly- (sub- benzene Base ether) non-solvent liquid medium in pass through the synthesis of poly- (phenylene ether) of oxidation coupling monohydric phenol.Poly- (the phenylene of product Ether) absolute number average molecular be 13,200 to 31,000 grams/mol.

The synthesis of two kinds of synthetic methods is also known.For example, the U.S. Patent No. of Izawa et al. is licensed to, 789,054 The method of the polymerization for the disubstituted phenol of 2,6- number is described, this method passes through in dimethylformamide or by toluene The disubstituted phenol solution of 2,6- that 15 to 35wt% are prepared with the in the mixed solvent of methanol composition, makes the solution in an area It carries out polymerizeing in domain while reaction mixture is maintained homogeneous solution, and polymeric liquid is delivered to another region to complete to gather Resulting polymers are precipitated when contract.Method describes that poly- (phenylene ether) of intrinsic viscosity at least 0.25 deciliter/gram can be generated, And in working Examples generated poly- (phenylene ether) at 25 DEG C, intrinsic viscosity range in chloroform 0.44 to 0.77 deciliter/gram.

There is still a need for preparation low molecular weight poly- (phenylene ether) method, wherein method reduce dialkylamine co-catalyst to Chemistry incorporation in poly- (phenylene ether), simplifies purifying and separating step, and eliminate to separate poly- (phenylene ether) And to the needs of multi-solvents.

Summary of the invention

A method of being used to form poly- (phenylene ether) copolymer, comprising: there are molecular oxygen, comprising metal ion and In the case where the polymerization catalyst and solvent of at least one amine ligand, by the monohydric phenol comprising 2- methyl -6- phenylphenol and Dihydric phenol is reacted to form the copolymer of 2- methyl -6- phenylphenol and dihydric phenol；Wherein copolymer has 1,000 to 10,000 Gram/mol absolute number average molecular；And wherein solvent includes the C of at least 95 weight percent based on solvent total weight₁- C₃Alcohol, C₁-C₃Alcohol is selected from the group being made of methanol, ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol.

A kind of poly- (phenylene ether) copolymer, is derived from monohydric phenol and dihydric phenol including 2- methyl -6- phenylphenol, And with 1,000 to 10,000 grams/mol of absolute number average molecular.Copolymer can be prepared by methods herein.It is poly- (phenylene ether) copolymer can have with flowering structure:

Wherein: R independently is methyl or two (normal-butyl) aminomethyls at each occurrence；Condition is that copolymer fifty-fifty wraps Containing two (normal-butyl) aminomethyls less than or equal to 0.005 weight percent based on copolymer weight；And x and y are each Independently 0 to 50 when appearance, condition is x and y and is 4 to 53.

A kind of curable compositions include thermosetting resin and poly- (phenylene ether) copolymer described herein.One kind passes through Curable compositions heating is enough the time and the temperature that are cured to obtain cured composition, and product may include Cured composition.

These and other described in detail below embodiment.

Specific embodiment

Present inventor have determined that can have the catalyst comprising mantoquita and amine and be used for the non-of poly- (phenylene ether) In the case where solvent, using the gas of molecule-containing keto, it is poly- (sub- that low molecular weight is prepared by the oxidation coupling of monohydric phenol and dihydric phenol Phenyl ether).Gained solid-liquid reaction mixture contain can with liquid phase separation and can handle to remove relict catalyst Poly- (phenylene ether) particle.Isolated liquid phase can reuse in the polymerization.Advantageously, it is produced by this method Poly- (phenylene ether) have poly- (phenylene ether) in dialkyl amino it is low chemistry incorporation.

The method for being used to form poly- (phenylene ether) copolymer, comprising: there are molecular oxygen, include metal ion and at least In the case where a kind of polymerization catalyst and solvent of amine ligand, by monohydric phenol and binary including 2- methyl -6- phenylphenol Phenol is reacted to form the copolymer of 2- methyl -6- phenylphenol and dihydric phenol；Wherein copolymer have 1,000 to 10,000 grams/ Mole absolute number average molecular；And wherein solvent includes the C of at least 95 weight percent based on solvent total weight₁-C₃ Alcohol, C₁-C₃Alcohol is selected from the group being made of methanol, ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol.

By continuously adding oxygen into the reaction mixture comprising monomer, solvent and polymerization catalyst, by the inclusion of 2- first The monomer of base -6- phenylphenol and the polymerization reaction of dihydric phenol form poly- (phenylene ether) copolymer.Can be used as air or Pure oxygen provides molecular oxygen (O₂).Polymerization catalyst is the metal complex comprising transition-metal cation.Metal cation can be with Ion and combinations thereof including VIB, VIIB, VIIIB or IB race from the periodic table of elements.Wherein it is possible to using chromium, manganese, cobalt, Copper and combination comprising at least one of above-mentioned ion.In some embodiments, metal ion is copper ion (Cu⁺And Cu^{2 +}).The metal salt that may be used as metal cation source includes stannous chloride, copper chloride, cuprous bromide, copper bromide, iodate Asia Copper, cupric iodide, cuprous sulfate, copper sulphate, four ammino of sulfuric acid be cuprous, cupric tetramminosulfate, cuprous acetate, copper acetate, propionic acid are sub- Copper, copper butyrate, lauric acid copper, palmitinic acid is cuprous, benzoic acid is cuprous and corresponding manganese salt and cobalt salt.It illustrates above instead of any The use of bright metal salt, it is also possible to add the water-soluble of metal or metal oxide and inorganic acid, organic acid or this acid Simultaneously corresponding metal salt or hydrate is formed in situ in liquid.Bromination is generated for example, cuprous oxide and hydrobromic acid can be added in situ It is cuprous.

Polymerization catalyst also includes at least one amine ligand.Amine ligand can be such as monoamine, alkylene diamine or packet Containing above-mentioned at least one combination.Monoamine include dialkyl group monoamine (such as dibutyl amine or DBA) and trialkyl monoamine (such as N, N- dimethylbutyl amine or DMBA).Diamines includes alkylene diamine, such as N, N'- di-t-butyl ethylene diamine or DBEDA.It is suitable The dialkyl group monoamine of conjunction include dimethylamine, di-n-propylamine, di-n-butylamine, two-sec-butylamines, two-tert-butylamines, diamylamine, two oneself Amine, dioctylamine, didecylamine, dibenzyl amine, Methylethyl amine, methyl butyl amine, dicyclohexylamine, N- phenylethanol amine, N- (p- methyl) phenylethanol amine, N- (2,6- dimethyl) phenylethanol amine, N- (p- chlorine) phenylethanol amine, N-ethylaniline, N- butylaniline, N- methyl -2-aminotoluene, N- methyl -2,6- dimethylaniline, diphenylamines etc. and combinations thereof.Three suitable alkane Base monoamine includes trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, butyldimethylamine, diethylamino phenyl amine etc. and combinations thereof.

Suitable alkylene diamine includes having those of the formula

(R^b)₂N-R^a-N(R^b)₂

Wherein R^aIt is substituted or unsubstituted residue of divalent；And each R^bIt independently is hydrogen or C₁-C₈Alkyl.One In a little examples, in above formula, two or three aliphatic carbon atoms form closure connection between two two amine nitrogen atoms (closest link).Specific alkylene diamine ligand includes wherein R^aFor dimethylene (- CH₂CH₂) or trimethylene (- CH₂CH₂CH₂Those of).R^bHydrogen, methyl, propyl, isopropyl, butyl or C can independently be₄-C₈α-tertiary alkyl.Alkylene two The example of amine ligand includes N, N, N', N' tetramethylethylened (TMED), N, N'- di-t-butyl ethylenediamine (DBEDA), N, N, N', N'- tetramethyl-l, 3- diaminopropanes (TMPD), N- methyl-1,3- diaminopropanes, N, N'- dimethyl -1,3- Diaminopropanes, N, N, N'- dimethyl -1,3- diaminopropanes, N- ethyl -1,3- diaminopropanes, N- methyl-l, 4- diamino Base butane, N, N'- trimethyl-l, 4- diaminobutane, N, N, N'- trimethyl-l, 4- diaminobutane, N, N, N', N'- tetramethyl Base-l, 4- diaminobutane, N, N, N', N'- tetramethyl-l, 5- 1,5-DAP and combinations thereof.In some embodiments, amine Ligand is selected from di-n-butylamine (DBA), N, N- dimethyl butylamine (DMBA), N, N'- di-t-butyl ethylenediamine (DBEDA) and its group It closes.Catalyst can be prepared in situ by mixing metal ion source (for example, cuprous oxide and hydrobromic acid) with amine ligand. In some embodiments, polymerization catalyst includes copper ion, bromide ion and N, N'- di-t-butyl ethylenediamine.

Solvent includes the C of at least 95 weight percent based on solvent total weight₁-C₃Alcohol, C₁-C₃Alcohol is selected from by methanol, second The group of alcohol, 1- propyl alcohol and 2- propyl alcohol composition.In the range, solvent may include the weight percent of at least 98,99 or 99.9 C₁-C₃Alcohol.Solvent may include less than 5 weight percent, and the weight percent of particularly less than 2,1 or 0.1 removes C₁-C₃Alcohol Solvent in addition.For example, removing C₁-C₃Solvent other than alcohol may include as metal ion, for example, Cu₂What the solution of O introduced Water, or as amine ligand, for example, the toluene that the solution of di-t-butyl ethylenediamine introduces.In some embodiments, C₁-C₃ Alcohol is methanol, and solvent includes the methanol of at least 99 weight percent.

Advantageously, the monomer and dihydric phenol comprising 2- methyl -6- phenylphenol are in C₁-C₃Alcohol (C₁-C₃Alcohol be selected from by methanol, The group of ethyl alcohol, 1- propyl alcohol and 2- propyl alcohol composition) in it is solvable, but it is anti-by the polymerization of 2- methyl -6- phenylphenol and dihydric phenol Poly- (phenylene ether) copolymer should be formed by C₁-C₃It is insoluble in alcohol.Therefore, poly- (phenylene ether) copolymer is in its formation Precipitating, which has limited absolute number average moleculars.It is poly- when being prepared in poly- (phenylene ether) solvent such as toluene by homogeneous polymerization When (phenylene ether), it is necessary to non-solvent dilution polymeric solution to precipitate poly- (phenylene ether).Advantageously, because in present invention side (phenylene ether) copolymer poly- in method precipitates during polymerization, therefore completely avoids post precipitation step.This is not only eliminated Method and step, and also avoid and distill related height with the solvent mixture for recycling single solvent (solvent and non-solvent) Cost of energy.

Poly- (phenylene ether) copolymer may include the repetitive unit and 1 derived from monohydric phenol of 80 to 99 weight percent To the repetitive unit derived from dihydric phenol of 20 weight percent.In the range, poly- (phenylene ether) copolymer may include The repetition derived from dihydric phenol of the repetitive unit and 5 to 15 weight percent derived from monohydric phenol of 85 to 95 weight percent Unit.

Dihydric phenol can have with flowering structure:

The R wherein occurred every time¹And R²And R³And R⁴Independently selected from by hydrogen, halogen, unsubstituted or substituted C₁-C₁₂ Alkyl (condition is that alkyl is not tertiary hydrocarbon base), C₁-C₁₂Alkylthio, C₁-C₁₂Alkyl oxygroup and C₂-C₁₂Halohydrocarbyl oxygroup (its In at least two carbon atoms halogen and oxygen atom are separated) composition group；Z is 0 or 1；And Y is selected from and is made of following item Group:

The R wherein occurred every time⁵-R⁸It independently is hydrogen, C₁-C₁₂Alkyl or C₁-C₆Alkylene, wherein the R occurred twice⁵ Together form C₄-C₁₂Alkylidene.In some embodiments, 1 z.The example of dihydric phenol includes 3,3', 5,5'- tetramethyl- Bis- (3- methyl -4- hydroxyphenyl) propane of 4,4'- biphenol, 2,2-, 2,2- bis- (3,5- dimethyl -4- hydroxyphenyl) propane, 1,1- Bis- (4- hydroxyphenyl) ethane of bis- (4- hydroxyphenyl) methane, 1,1-, bis- (4- hydroxyphenyl) propane of 2,2-, bis- (4- hydroxyphenyl) fourths of 2,2- Bis- (4- hydroxyphenyl) octanes of alkane, 2,2-, bis- (4- hydroxyphenyl) propane of 1,1-, bis- (4- the hydroxyphenyl)-normal butanes of 1,1-, bis- (4- hydroxyls Phenyl) toluene, bis- (the 4- hydroxy-3-methyl phenyl) propane of 2,2-, 1,1- bis- (4- hydroxy-3-methyl phenyl) hexamethylenes, 1,1- Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) pentamethylene, 1,1- bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) hexamethylenes, the bis- (4- of 1,1- Hydroxy-3-methyl phenyl) cycloheptane, bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) cycloheptane of 1,1-, the bis- (4- hydroxyl -3- first of 1,1- Base phenyl) cyclooctane, bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) cyclooctane of 1,1-, bis- (the 4- hydroxy-3-methyl phenyl) rings of 1,1- Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) cyclononane of nonane, 1,1-, 1,1- bis- (4- hydroxy-3-methyl phenyl) cyclodecane, 1,1- Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) cyclodecane, bis- (4- hydroxy-3-methyl phenyl) the ring hendecanes of 1,1-, bis- (the 4- hydroxyls of 1,1- Base -3,5- 3,5-dimethylphenyl) ring hendecane, bis- (the 4- hydroxy-3-methyl phenyl) cyclododecanes of 1,1-, 1,1- it is bis- (hydroxyl -3 4-, 5- 3,5-dimethylphenyl) cyclododecane, bis- (4- hydroxyl -3- tert- butylbenzene base) propane of 1,1-, the bis- (4- hydroxyl -2,6- dimethyl of 2,2- Phenyl) propane, bis- (4- hydroxyl -3- bromophenyl) propane of 2,2-, bis- (4- hydroxyphenyl) pentamethylene of 1,1-, 1,1- bis- (4- hydroxyphenyls) Hexamethylene, 2,2', the bromo- 4,4'- biphenol of 6,6'- tetramethyl -3,3', 5,5'- tetra-, 2,2', 5,5'- tetramethyl -4,4'- bis-phenol Or include above-mentioned at least one combination.In some embodiments, dihydric phenol includes bis- (3, the 5- dimethyl -4- hydroxyls of 2,2- Base phenol) propane.

The absolute number average molecular of poly- (phenylene ether) copolymer is 1,000 to 10,000 grams/mol.In the range, Absolute number average molecular can be greater than or equal to 1,500,2,000 or 2,700 grams/mol, and be less than or equal to 8,000, 5,000,4,000 or 3,000 grams/mol.In some embodiments, copolymer is with 1,000 to 5,000 gram/mol Absolute number average molecular, specifically, 1,000 to 4,000,1,000 to 3,000 or 2,700 to 3,000 gram/mol.

In some embodiments of method, the total weight based on monohydric phenol and dihydric phenol, monohydric phenol includes less than 0.5 weight 2- and 6- in phenol ring for measuring percentage have the monohydric phenol of identical substituent group.In the range, monomer, which may include, is less than Or there is the monohydric phenol of identical substituent group equal to 2- and 6- in phenol ring of 0.1 weight percent or zero.In some implementations It is 2,6- dimethlbenzene or 2,6- diphenyl benzene in the 2- and 6- monohydric phenols with identical substituent group of phenol ring in mode Phenol.

When amine ligand includes secondary amine, when such as di-n-butylamine, in end, the benzylic positions of unitary phenol unit are by some secondary amine Be introduced to poly- (phenylene ether).As follows, covalently bound monoamine groups are present in terminal units as aminomethyl The ortho position of phenol oxygen:

It can pass through¹H-NMR spectroscopy determines the amount of covalently bound unitary amido.Covalently bound unitary amido can be with The oxidation stability of poly- (phenylene ether) is negatively affected, and the Huang of poly- (phenylene ether) can be caused in heat ageing Change.Advantageously, method causes compared with the method for wherein generating poly- (phenylene ether) copolymer by homogeneous solution polymerization, unitary Incorporation of the secondary amine into poly- (phenylene ether) copolymer is reduced.Therefore, when amine ligand includes two (C₁-C₆Alkyl) amine when, 2- first The copolymer of base -6- phenylphenol and dihydric phenol includes the two (C less than 0.005 weight percent based on copolymer weight₁- C₆Alkyl) amino.

In some embodiments, dihydric phenol includes bis- (3, the 5- dimethyl -4- hydroxyl phenol) propane of 2,2-；It is at least one Amine ligand includes two (normal-butyl) amine；Solvent includes the methanol of at least 99 weight percent；2- methyl -6- is formd by method The copolymer of phenylphenol and bis- (3,5- dimethyl -4- hydroxyl phenol) propane of 2,2-；And copolymer includes to be based on copolymer Two (normal-butyl) amino less than 0.005 weight percent of weight.

It also discloses through poly- (phenylene ether) copolymer prepared by methods herein.Therefore, poly- (phenylene ether) is total Polymers is derived from monohydric phenol and dihydric phenol including 2- methyl -6- phenylphenol, and has 1,000 to 10,000 gram/mol Absolute number average molecular.In the range, absolute number average molecular can be greater than or equal to 1,500,2,000 or 2,700 Gram/mol, and it is less than or equal to 8,000,5, and 000,4,000 or 3,000 gram/mol.In some embodiments, gather (phenylene ether) copolymer has 1,000 to 5,000 gram/mol of absolute number average molecular, specifically, 1,000 to 4,000, 1,000 to 3,000 or 2,700 to 3,000 grams/mol.For example, monohydric phenol can be 2- methyl -6- phenylphenol and 2,6- The combination of dimethlbenzene, and poly- (phenylene ether) can be the absolute number average molecular with 1,000 to 3,000 gram/mol 2- methyl -6- phenylphenol, 2,6- dimethlbenzene and bis- (3,5- dimethyl -4- hydroxyl phenol) propane of 2,2- ternary polymerization Object.As described in Working Examples part, pass through¹H-NMR determines absolute number average molecular.It is by poly- (phenylene ether) Copolymer¹Integral area under the formant of H-NMR spectrum calculates acquisition, the molar concentration with the substance for corresponding to peak It is proportional.

Poly- (phenylene ether) copolymer may include the repetitive unit and 1 derived from monohydric phenol of 80 to 99 weight percent To the repetitive unit derived from dihydric phenol of 20 weight percent.In the range, poly- (phenylene ether) copolymer may include The repetition derived from dihydric phenol of the repetitive unit and 5 to 15 weight percent derived from monohydric phenol of 85 to 95 weight percent Unit.

In some embodiments of poly- (phenylene ether) copolymer, the total weight based on monohydric phenol and dihydric phenol, unitary Phenol includes the monohydric phenol for having identical substituent group less than 2- and 6- in phenol ring of 0.5 weight percent.In the range, one First phenol may include less than or equal to 0.1 weight percent or zero 2- and 6- in phenol ring have identical substituent group one First phenol.In some embodiments, 2- and 6- of the phenol ring monohydric phenols with identical substituent group be 2,6- dimethlbenzene or Person's 2,6- diphenyl phenol.

In some embodiments, poly- (phenylene ether) copolymer has a structure that

Wherein: R independently is methyl or two (normal-butyl) aminomethyls at each occurrence；Condition is that copolymer fifty-fifty wraps Containing two (normal-butyl) aminomethyls less than or equal to 0.005 weight percent based on copolymer weight；And x and y are each Independently 0 to 50 when appearance, condition is x and y and is 4 to 53.In some implementations of above poly- (phenylene ether) copolymer In mode, x and y's and be 8 to 20.

As difunctionality, tool there are two reactive phenolic group, poly- (phenylene ether) copolymer be preferably suited comprising Reactive component is used as in the curable compositions of thermosetting resin.Therefore, curable compositions include thermosetting resin, this paper's Poly- (phenylene ether) copolymer.Thermosetting resin can be (for example) epoxy resin, cyanate ester resin, bismaleimide tree Rouge, polybenzoxazine resin, vinyl, phenol resin, alkyd resin, unsaturated polyester resin include above-mentioned thermosetting property tree The combination of at least one of rouge.It can form polyglycidyl ether by reacting for phenol or polyphenol and epichlorohydrin and produce conduct The useful epoxy resin of thermosetting resin.The example that useful phenol is produced for epoxy resin includes the bisphenol-A replaced, bis-phenol F, quinhydrones, resorcinol, three-(4- hydroxyphenyl) methane and the novolac resin derived from phenol or o-cresol.It can also lead to Aromatic amine is crossed, as para-aminophenol or methylene diphenylamines produce epoxy with reacting for epichlorohydrin to form poly epihydric alcohol amine Resin.

By the way that with crosslinking agent, commonly referred to as curing agent or curing agent solidification, epoxy resin can be converted into solid, infusibility With insoluble three-dimensional network.Curing agent is catalytic or coreactivity.Coreactivity curing agent has can be with asphalt mixtures modified by epoxy resin The epoxy reaction of rouge is to form the active hydrogen atom of crosslinked resin.Active hydrogen atom can reside in functional group, including primary Or secondary amine, phenol, mercaptan, carboxylic acid or carboxylic acid anhydride.The example of coreactivity curing agent for epoxy resin include aliphatic series and Cycloaliphatic amine and with the amine-functional adduct of epoxy resin, Mannich base, aromatic amine, polyamide, amide amine, phenol alkylamine (phenalkamines), dicyandiamide, polycarboxylic acid-functional polyesters, carboxylic acid anhydride, amine-formaldehyde resin, phenol formaldehyde resin, Polysulfide, polymercaptan and the combination comprising at least one of above-mentioned coreactivity curing agent.Catalytic curing agent is used as epoxy The initiator of resin homopolymerization or accelerator as coreactivity curing agent.The example of catalytic curing agent includes tertiary amine, such as 2-ethyl-4-methylimidazole, lewis acid, such as boron trifluoride and latent cationic cure catalyst, such as diaryl iodonium salt.

Thermosetting resin can be cyanate.Cyanate is with cyanic acid the ester group (- O-C by oxygen atoms bond to carbon ≡ N) compound, i.e., with C-O-C ≡ N base compound.Generation can be reacted by cyanogen halides and phenol or substituted phenol The cyanate useful as thermosetting resin.The example of useful phenol is included in epoxy resin, such as bisphenol-A, Bisphenol F and is based on Bis-phenol used in the production of phenol or the novolac resin of o-cresol.Cyanogen is prepared for by polymerization/ring trimerization of cyanate Acid esters prepolymer.The prepolymer prepared from cyanate and diamines can also be used.Thermosetting resin can be bismaleimide. Can be by monomer bismaleimide and nucleopilic reagent, such as the reaction of diamines, amino-phenol or amino phenylhydrazide, or pass through Bismaleimide and hexadiene bisphenol-A react to generate bimaleimide resin.Thermosetting resin can be vinyl Resin.Vinylite is the monomer or polymer with alkenyl degree of unsaturation.The example of vinylite includes unsaturated poly- Ester, styrene monomer, (methyl) acrylate, allyl ether, vinyl ethers and include above-mentioned at least one combination.

By curable compositions as defined herein heating being enough time for being cured and temperature is solidified Composition.In solidification, the space polymers network of crosslinking is formd.For specific thermosetting resin, for example, (methyl) third Alkene acid ester resin can also be cured by being radiated under enough wavelength and time with actinic radiation.

Due to the presence of poly- (phenylene ether) copolymer, cured composition can have useful in various products appoint What some beneficial physical property absorbs, high T including excellent impact strength, hydrolytic stability, low moisture_gWith excellent Jie Electrical property.Therefore, product may include by the way that curable compositions as defined herein heating is enough the time being cured With temperature cured composition obtained.

It further illustrates the present invention by following implementation to disclose, following implementation is not intended to limit claim