JP4916840B2 - Aromatic polycarbonate copolymer resin and process for producing the same - Google Patents

Description

  The present invention relates to a method for producing an aromatic polycarbonate copolymer resin composed of an aromatic polycarbonate resin component and a thermoplastic resin component.

  Aromatic polycarbonate resin is a kind of engineering plastic used in a wide range of fields, and is excellent in heat resistance, impact resistance, transparency, dimensional stability, flame retardancy, and the like. However, this resin is more expensive than general-purpose resins, has low fluidity under the same molding conditions and poor moldability, poor molded product productivity, low chemical resistance, and impact strength. Due to problems such as large thickness dependency, it is used as an alloy with various resins.

  In recent years, from the viewpoint of global warming, research has been actively conducted to replace plastics derived from fossil-derived resources with plastics derived from plant materials. And the alloy of these plant origin plastics and aromatic polycarbonate resin is also one of the main subjects. In addition, the use of biodegradable resins and their polymer alloys is increasing from the viewpoint of global environmental conservation.

A melt kneading method is widely used for the production of polymer alloys. In this method, the compatibility between the resins is important, and it cannot be said that the resin is sufficiently mixed simply by melting the resin and stirring and mixing. It is. Therefore, complicated steps are required for producing a polymer alloy, such as adding a compatibilizing agent suitable for the resin to be alloyed, or synthesizing a copolymer at the polymer production stage. In particular, random copolymerization cannot produce the characteristics of each copolymerized polymer, and it is necessary to obtain a block copolymer having an appropriate block length, so that the production becomes more complicated than a normal process. .
In addition, there is an attempt to produce a copolymer resin composition from polymers using chemical bond exchange reaction, but under normal conditions, the exchange reaction is insufficient and copolymerization does not proceed, and a large amount of There were problems such as requiring a catalyst, high temperature, and long reaction time (Non-patent Document 1).

  As a technique for producing an alloy of a polycarbonate resin and another resin, Non-Patent Document 1 and Patent Document 1 disclose a method of transesterifying an aromatic polycarbonate resin and a polyester resin, and Patent Documents 2 and 3 disclose a phase change. A method for producing an alloy of an aromatic polycarbonate resin and a polylactic acid resin by adding a solubilizer is disclosed. Further, Patent Document 4 discloses a method of alloying an aromatic aliphatic polycarbonate resin and a polylactic acid resin, and Patent Document 5 discloses a method of copolymerizing lactide in the presence of an aromatic polycarbonate resin. Discloses a method of copolymerizing an aromatic polycarbonate resin and a polylactic acid resin, respectively.

However, the methods of Patent Document 1 and Non-Patent Document 1 require the addition of a large amount of catalyst, a high temperature, and a long reaction time in order to promote the transesterification reaction. Further, in Patent Documents 2 and 3, there is a problem that not only the compatibilizing agent has to be added but the cost is increased, and the physical properties are not stable because the dispersion state of the alloy changes depending on the kneading conditions and molding conditions. In the method of Patent Document 4, the heat resistance is not sufficiently improved. In Patent Document 5, only a resin having an opaque and low glass transition temperature can be obtained. Moreover, in patent document 6, there existed a problem that reaction was performed in the organic solvent, operation was complicated, and it was not suitable for mass production.
Proceedings of the annual meeting of the Society of Polymer Science, Japan, Vol.55, No.1, 935 (2006) JP-T-2006-514703 JP 2006-028299 A JP 2006-131828 A JP-A-11-140292 JP 7-82369 A JP-A-9-216942

  The present invention solves the above-mentioned problems, and usually improves the exchange reaction between a carbonate bond and an ester bond, which is very difficult, and does not require the addition of a compatibilizing agent. It is an object of the present invention to provide a method for producing an aromatic polycarbonate copolymer resin excellent in heat resistance and fluidity.

  As a result of intensive investigations, the present inventors have used a compound (C) having an active hydrogen-containing functional group, whereby an aromatic polycarbonate resin (A) and a thermoplastic resin (B) or a raw material compound of a thermoplastic resin ( From B ′), it was found that an aromatic polycarbonate copolymer resin containing an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component can be produced.

That is, the gist of the present invention is as follows.
(1) In the method for producing an aromatic polycarbonate copolymer resin containing an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component, the thermoplastic resin (B) component is a polylactic acid resin, and active hydrogen Production of aromatic polycarbonate copolymer resin characterized by polymerizing raw material compound (B ′) of thermoplastic resin after reacting compound (C) having functional group and aromatic polycarbonate resin (A) Method.
(2) In the method for producing an aromatic polycarbonate copolymer resin containing an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component, the thermoplastic resin (B) component is a polylactic acid resin, and active hydrogen A process for producing an aromatic polycarbonate copolymer resin, comprising reacting a compound (C) having a functional group with an aromatic polycarbonate resin (A) and then reacting a thermoplastic resin (B).
(3) The method for producing an aromatic polycarbonate copolymer resin according to (1) or (2), wherein the functional group of the compound (C) having an active hydrogen-containing functional group is a hydroxyl group.
(4) The method for producing an aromatic polycarbonate copolymer resin according to any one of (1) to ( 3), wherein the reaction is performed in a molten state.
(5) The reaction is performed in the presence of 0.001 to 0.1 parts by mass of a transesterification catalyst (D) with respect to 100 parts by mass of the obtained aromatic polycarbonate copolymer resin (1) to ( 4 ) The manufacturing method of the aromatic polycarbonate copolymer resin in any one of.
(6) The method for producing an aromatic polycarbonate copolymer resin according to any one of claims 1 to 5 , wherein a chain extension reaction is performed after the reaction.
(7) An aromatic polycarbonate copolymer resin obtained by the production method according to any one of (1) to ( 6 ).

Usually, an exchange reaction between a carbonate bond and an ester bond is very difficult as apparent from Non-Patent Document 1, but the present inventors have used a compound (C) having an active hydrogen-containing functional group. The present inventors have found that the exchange reaction proceeds relatively easily and an aromatic polycarbonate copolymer resin can be produced. By the production method of the present invention, an aromatic polycarbonate copolymer resin can be produced simply and efficiently without using complicated production steps using conventional production equipment. Furthermore, the use of polylactic acid resin, which is a plant-derived polymer , as the thermoplastic resin (B) contributes greatly to the prevention of global warming because it is carbon-neutral as much as the degree of plant, and also saves petroleum resources. The industrial utility value is extremely high.

Hereinafter, the present invention will be described in detail.
The aromatic polycarbonate copolymer resin of the present invention contains an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component.
The aromatic polycarbonate resin (A) is a resin represented by the following formula, and a bisphenol-based polycarbonate resin is exemplified.
(R represents an aromatic hydrocarbon compound, but may contain atoms other than carbon and hydrogen.)

  Specific examples of the bisphenol-based polycarbonate resin include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-methyl-2-hydroxyphenyl). ) Methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -2-ethyl Xanthine, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-methyl-4-hydroxyphenyl) methane, 4,4′-biphenol, 2,2-bis (4 -Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) ) Octane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4) Hydroxyphenyl) propane, bisphenolfluorene, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 4,4 ′-[1,4-phenylene-bis (2 -Propylidene) -bis (3-methyl-4-hydroxyphenyl)], 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenyl ether, bis (2-hydroxyphenyl) Methane, 2,4′-methylenebisphenol, bis (3-methyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-5-methylphenyl) ethane, 1 , 1-bis (4-hydroxyphenyl) -3-methylbutane, bis (2-hydroxy-3, 5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) Pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane, 3,3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane, 2,2-bis (2-hydroxy-3, 5-dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) nonane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5 -Dimethyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) de Bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) ) Cyclohexane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1 -Bis (3,5-ditert-butyl-4-hydroxyphenyl) methane, 1,1-bis (3,5-disec-butyl-4-hydroxyphenyl) methane, 1,1-bis (3-cyclohexyl) -4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-ditert-butylphenol) ) Ethane, bis (3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) propane, bis (2-hydroxy-3,5-di) tert-butyl-6-methylphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (2-hydroxy) -5-fluorophenyl) methane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) ) Propane, bis (3-fluoro-4-hydroxyphenyl) -phenylmethane, bis (3-fluoro-4-hydroxyphenyl)-(p-fluoro) Phenyl) methane, bis (4-hydroxyphenyl)-(p-fluorophenyl) methane, 2,2-bis (3-chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3,5 -Dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-nitro-4-hydroxyphenyl) propane, 3,3′-dimethyl-4,4′-biphenol, 3,3 ′ , 5,5′-tetramethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetratert-butyl-4,4′-biphenol, bis (4-hydroxypheny ) Ketone, 3,3′-difluoro-4,4′-biphenol, 3,3 ′, 5,5′-tetrafluoro-4,4′-biphenol, bis (4-hydroxyphenyl) dimethylsilane, bis (3 -Methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (2,3,5-trimethyl-4-hydroxyphenyl) -phenylmethane, 2,2-bis ( 4-hydroxyphenyl) dodecane, 2,2-bis (3-methyl-4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) dodecane, 1,1-bis (3 -Tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-ditert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-ditert-butylphenyl) ) Ethane, isatin bisphenol, isatin biscresol, 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-biphenol, bis (2-hydroxyphenyl) methane, 2,4′- Methylene bisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane, bis (2-hydroxy-3-allylphenyl) methane, 1, 1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-5-tert- Butylphenyl) ethane, bis (2-hydroxy-5-phenylphenyl) methane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis (2-methyl-4-hydroxy) -5-cyclohexylphenyl) methane, 2,2-bis (4-hydroxyphenyl) pentadecane, 2,2-bis (3-methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl- 4-hydroxyphenyl) pentadecane, 1,2-bis (3,5-ditert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5-ditert-butylphenyl) methane, 2,2 -Bis (3-styryl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1- (p-ni Rophenyl) ethane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl) phenylmethane, bis (3,5-difluoro-4-hydroxyphenyl) diphenylmethane, Bis (3-fluoro-4-hydroxyphenyl) diphenylmethane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 3,3 ′, 5,5′-tetra-tert-butyl-2,2′- Biphenol, 2,2'-diallyl-4,4'-biphenol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl)- 3,3,5,5-tetramethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,4- Limethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5-ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3 , 5-trimethyl-cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3 , 3,5-trimethyl-cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane Xanthine, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dibromo-4-hydroxyphenyl)- 3,3,5-trimethyl-cyclohexane, bis (4-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-diethyl) -4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl) -4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) Sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, e.g., 2,4-dihydroxydiphenyl sulfone.

In the present invention, the thermoplastic resin (B) needs to be a polylactic acid resin which is a plant-derived or biodegradable polymer from the viewpoint of global environmental conservation. As a method for introducing an active hydrogen-containing functional group, a compound having a functional group to be introduced is used as an initiator for polymer polymerization, a copolymerization component, a coupling reaction, or a polymer having a functional group to be introduced is dissolved. It can be obtained by a polymerization method or the like.

In the present invention, since the thermoplastic resin (B) is a polylactic acid resin, the raw material compound (B ′) is a compound such as lactic acid, lactide, lactic acid ester, or lactic acid oligomer.

  The molecular weight of the thermoplastic resin (B) is not particularly limited, but the total amount of the active hydrogen-containing functional groups of the compound to be mixed and reacted is larger than the molar amount of the polycarbonate with respect to the molar amount of the aromatic polycarbonate resin (A). It is preferable. When the amount is less than the equimolar amount, the degree of multi-blocking becomes small.

  In the present invention, the compound (C) having an active hydrogen-containing functional group is preferably a compound having two or more active hydrogen-containing functional groups and one or more ring structures. Examples of the active hydrogen-containing functional group include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, and a thiol group. From the viewpoint of easy control of reaction, difficulty in coloring, and availability, Is preferred. Specific examples of the compound (C) having an active hydrogen-containing functional group include 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, tricyclodecane dimethanol, adamantanediol, isosorbide, 4 -Hydroxyphenyl-2-ethyl alcohol, bisphenol A, bisphenol S, bisphenol A ethylene glycol adduct, bisphenol S ethylene glycol adduct, 4-hydroxycyclohexanecarboxylic acid, p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid Terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tricyclodecanedicarboxylic acid, adamantanedicarboxylic acid, 1,4-phenylenediamine, 1 3-phenylene diamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, norbornane diamine, tricyclodecane diamine, adamantane diamine. Of these, alicyclic compounds are preferably used.

As a method for producing an aromatic polycarbonate copolymer resin containing the aromatic polycarbonate resin (A) component and the thermoplastic resin (B) component of the present invention,
(1) Method of polymerizing raw material compound (B ′) of thermoplastic resin after reacting compound (C) having an active hydrogen-containing functional group and aromatic polycarbonate resin (A) [ I ]
(2) The method [ II ] of reacting the thermoplastic resin (B) after reacting the compound (C) having an active hydrogen-containing functional group with the aromatic polycarbonate resin (A).

In each of the above methods, the reaction is preferably a solvent-free system, and each component is preferably stirred and mixed in a molten state. The reaction temperature is preferably 180 to 250 ° C, more preferably 190 to 240 ° C, and more preferably 200 to 230 ° C. If the reaction temperature is less than 180 ° C., it is difficult to carry out the reaction uniformly and the reaction efficiency is low. On the other hand, when the reaction temperature exceeds 250 ° C., the thermal decomposition and coloring of the resin become remarkable, which is not preferable.
In the methods [I] and [II] , the reaction time with the compound (C) having an active hydrogen-containing functional group is preferably 5 minutes to 12 hours, and more preferably 10 minutes to 8 hours. . When the reaction time is less than 5 minutes, the reaction becomes insufficient when the reaction conditions are mild, and when the reaction conditions are extreme, the reaction is difficult to control or the coloring becomes remarkable. When the reaction time exceeds 12 hours, the productivity is low and the cost is high, or the resulting copolymer resin is markedly colored. In the reaction performed after reacting with the compound (C) having an active hydrogen-containing functional group, the reaction time is preferably 5 minutes to 12 hours, and more preferably 10 minutes to 8 hours. When the reaction time is less than 5 minutes, the reaction becomes insufficient when the reaction conditions are mild, and when the reaction conditions are extreme, the reaction is difficult to control or the coloring becomes remarkable. When the reaction time exceeds 12 hours, the productivity is low and the cost is high, or the resulting copolymer resin is markedly colored.

In each of the above methods, the mass ratio ((A / B) or (A / B ′)) between the aromatic polycarbonate resin (A) and the thermoplastic resin (B) or the raw material compound (B ′) is 10/90. It is preferably ˜90 / 10, more preferably 20/80 to 80/20.
The addition amount of the compound (C) having an active hydrogen-containing functional group is the total mass ((A + B) or (A + B ′)) of the aromatic polycarbonate resin (A) and the thermoplastic resin (B) or the raw material compound (B ′). The content is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

  In the production method of the present invention, a transesterification catalyst (D) can be added as necessary. Examples of the transesterification catalyst include tin octylate, tetrabutyl titanate, tetraisopropyl titanate, antimony trioxide, and germanium dioxide, and tin octylate is preferably used. The amount of the transesterification catalyst (D) added is preferably 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate copolymer resin to be produced. If the addition amount is less than 0.001 part by mass, the effect of addition is poor, and if it exceeds 0.1 part by mass, the thermal stability of the polycarbonate copolymer resin to be produced is reduced, so an additional catalyst deactivator or the like is required. .

  In the production method of the present invention, in order to increase the molecular weight of the polycarbonate copolymer resin, the polycarbonate resin (A), the thermoplastic resin (B) or the raw material compound (B ′), the compound having an active hydrogen-containing functional group (C After the reaction (2), a chain extension reaction can be performed using a chain extender.

  Examples of the chain extender include compounds having two or more functional groups, and examples of the functional group include isocyanate, epoxy, acid anhydride, acid chloride, and oxazoline. Specifically, tolylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, methylenebiscyclohexyl diisocyanate, bisisocyanatomethylcyclohexane Diisocyanates such as, bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol fluorene glycidyl ether, bisphenoxyethanol full orange glycidyl ether, resorcinol diglycidyl Ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, diglycidyl terephthalic acid, diglycidyl isophthalic acid, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Glycidyl ether, naphthalene tetracarboxylic acid anhydride, dioxotetrahydrofuranylmethylcyclohexene dicarboxylic acid anhydride, pyromellitic anhydride, oxydiphthalic acid anhydride, biphenyl tetracarboxylic acid anhydride, benzophenone tetracarboxylic acid anhydride, diphenyl sulfone tetracarboxylic acid Anhydride, tetrafluoroisopropylidenediphthalic anhydride, terphenyl ester Acid anhydrides such as lacarboxylic acid anhydride, cyclobutanetetracarboxylic acid anhydride, carboxymethylcyclopentanetricarboxylic acid anhydride, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples thereof include alicyclic carboxylic acids such as sebacic acid and cyclohexanedicarboxylic acid and acid chlorides thereof, and bisoxazolines such as 2,2 ′-(1,3-phenylene) bis-2-oxazoline, among which diisocyanate and diglycidyl. Ether and bisoxazoline are particularly preferred because of their high reactivity and easy handling. If the amount is small, a compound containing 3 or more functional groups may be used in combination.

  The type of chain extender is appropriately selected depending on the type of functional group of the compound (C) having an active hydrogen-containing functional group. For example, when the functional group (C) is an alcoholic hydroxyl group, the chain extender is preferably a diisocyanate, and when a phenolic hydroxyl group is produced by an ester carbonate exchange reaction, diglycidyl ether or bisoxazoline is preferred. When the functional group (C) is a carboxyl group, diglycidyl ether and bisoxazoline are preferred. When the functional group of (C) is an amino group, diisocyanate and diglycidyl ether are preferable, but when a phenolic hydroxyl group is generated by an ester carbonate exchange reaction, diglycidyl ether and bisoxazoline are preferable.

  The addition amount of the chain extender is such that the ratio of the functional group amount of the chain extender to the terminal functional group amount of the polycarbonate copolymer resin to be chain extended (extender / copolymer resin) is 0.98 to 1.1. It is preferable that When there are too many chain extenders, it is necessary to add a compound having a plurality of functional groups and re-extend. If the amount is too small, the polycarbonate copolymer resin cannot be made sufficiently high in molecular weight.

The reaction temperature of the chain extension reaction is preferably not less than the melting point or flow initiation temperature of the polycarbonate copolymer resin and not more than 230 ° C., more preferably the melting point or flow initiation temperature + 5 ° C. or more and 220 ° C. or less, more preferably Melting point or flow starting temperature + 10 ° C. or higher and 210 ° C. or lower. If the reaction temperature is not higher than the melting point or flow start temperature of the polycarbonate copolymer resin composition, it is difficult to proceed the reaction uniformly and the reaction efficiency is low, which is not preferable. On the other hand, when the reaction temperature exceeds 230 ° C., coloring due to side reaction becomes remarkable during the chain extension reaction, which is not preferable.
The chain extension reaction time is preferably 3 minutes to 2 hours, more preferably 5 minutes to 1 hour. When the reaction time is less than 3 minutes, the reaction is insufficient, and when it exceeds 2 hours, side reactions and coloring become remarkable.

  By performing the chain extension reaction, the weight average molecular weight of the polycarbonate copolymer resin can be increased to 20,000 or more. If the weight average molecular weight is 20,000 or less, the strength as a resin may not be sufficiently high. The weight average molecular weight is preferably 50,000 or more, and more preferably 100,000 or more.

  In the production method of the present invention, the reaction may be carried out by adding various additives such as an antioxidant as long as the reaction is not significantly inhibited.

Hereinafter, the present invention will be described specifically by way of examples. The characteristics of the aromatic polycarbonate copolymer resin were measured by the following method.
(1) Weight average molecular weight The weight average molecular weight was measured using gel permeation chromatography (GPC) equipped with a differential refractometer. Hexafluoroisopropanol containing 10 mM sodium trifluoroacetate was used as an eluent, and the weight average molecular weight was converted using polymethyl methacrylate (manufactured by Polymer Laboratories) as a standard sample.

(2) Block length of each component in copolymer resin The block length of each component in the aromatic polycarbonate copolymer resin was measured using a NMR apparatus (Lambda 300WB manufactured by JEOL) with a sample dissolved in deuterated chloroform. Were measured by proton and carbon NMR measurement at 75 MHz, and the abundance ratio of each component was calculated from the obtained spectrum.
The calculation of segment length proton and carbon attribution and each component of the aromatic polycarbonate copolymer resin, and 1 proton NMR spectrum of a copolymer resin obtained in Example 1 -1, the same resin Carbon NMR The spectrum diagram 2 was exemplified and the measurement was performed as follows.
As shown in FIG. 1, a peak (4.4 ppm) derived from a methine group adjacent to a terminal hydroxyl group derived from polylactic acid is not observed so much, and a significant portion of the terminal is a hydroxyl group derived from polycarbonate (in this case, the terminal hydroxyl group). The peak of the benzene ring hydrogen at the ortho position of the phenolic hydroxyl group was 6.7 ppm. This is because the end of the polymer was changed from polylactic acid to polycarbonate due to the exchange reaction between the carbonate bond and the terminal hydroxyl group of polylactic acid.
Moreover, as shown in FIG. 2, the peak derived from the structure considered that the polylactic acid unit couple | bonded next to the polycarbonate unit was observed. One is bound by a carbonate group, a peak derived from carbonate group carbon (153.1 ppm), and the other is bound by an ester group, and a peak derived from ester group carbon (168.8 ppm) is observed. It was. The peak of carbonate group carbon in the normal polycarbonate is (152.1 ppm), and the peak derived from ester group carbon in the polylactic acid chain is (169.6 ppm). Moreover, the peak derived from the aromatic ring carbon of the polycarbonate adjacent to polylactic acid was also shifted. These are considered to be caused by an exchange reaction between the hydroxyl group at the polylactic acid terminal and the carbonate bond of the polycarbonate.
From the above NMR measurement results, the polylactic acid block segment length and the polycarbonate block segment length were calculated from the amount of the polycarbonate-polylactic acid adjacent structure and the amount of the terminal group, and the results are shown in Table 1.
In other examples, the same measurement was performed to calculate the molecular weight and the block length.

The compounds used in the examples are as follows.
Aromatic polycarbonate resin (A): Caliber 200-13 manufactured by Sumitomo Dow
Thermoplastic resin raw material compound (B ′): L-lactide, Musashino Chemical Laboratory thermoplastic resin (B): Polylactic acid, manufactured by NatureWorks, weight average molecular weight 180,000, D isomer 1.1%

Example 1 -1
Using a lab plast mill manufactured by Toyo Seiki, 60 g of aromatic polycarbonate resin and 4.4 g of bisphenol A were reacted at 230 ° C. in a nitrogen stream, and the resulting reaction product was collected and pulverized. Add 21.5 g of this reaction product and 80 g of lactide in a glass polymerization tube, heat to 190 ° C., and with all components melted, add 20 μl of tin octylate and react for 1 hour to obtain an aromatic polycarbonate copolymer resin. It was.

Example 1-2
Payout the resin obtained in Example 1 -1, 190 ° C., under a nitrogen stream, isophorone diisocyanate (IPDI, bisphenol A and equimolar amounts) were added and reacted for 30 minutes, the chain-extended aromatic polycarbonate copolymer resin And recovered.

Example 2 -1
Using a lab plast mill manufactured by Toyo Seiki Co., Ltd., 60 g of aromatic polycarbonate resin and 6 g of tricyclodecane dimethanol were reacted at 230 ° C. in a nitrogen stream, and the resulting reaction product was recovered and pulverized. In a glass polymerization tube, 44 g of this reaction product and 60 g of lactide were added, heated to 190 ° C., and with all components melted, 20 μl of tin octylate was added and reacted for 1 hour to obtain an aromatic polycarbonate copolymer resin.

Example 2-2
The resin obtained in Example 2 -1, 190 ° C., under a nitrogen stream, BAGE (approximately equimolar amounts relative to tricyclodecanedimethanol) reacting added 30 minutes, aromatic polycarbonate copolymer obtained by chain extension The resin was dispensed and collected.

Example 3-1
Using a Laboplast mill manufactured by Toyo Seiki, 12 g of aromatic polycarbonate resin, 45 g of polylactic acid, and 3 g of tricyclodecane dimethanol were heated and melted at 230 ° C. in a nitrogen stream. After the temperature was lowered to 210 ° C., 50 μl of tributyl titanate was added and reacted with stirring for 2 hours to obtain an aromatic polycarbonate copolymer resin.

Example 3-2
Example 3 After the temperature of the resin obtained in -1 was lowered to 190 ° C., bisphenol fluorenediglycidyl ether (BPFG, tricyclodecane dimethanol and an equimolar amount) was added thereto and reacted for 30 minutes in a nitrogen stream. The chain-extended aromatic polycarbonate copolymer resin was dispensed and recovered.

Comparative Example 1
In a glass polymerization tube, 60 g of L-lactide was added, the temperature was raised to 190 ° C. under a nitrogen stream, and 20 μl of tin octylate was added and reacted for 1 hour to synthesize polylactic acid having a weight average molecular weight of 210,000. To this was added 40 g of aromatic polycarbonate resin, and the system was heated to 230 ° C. When the aromatic polycarbonate resin was melted and reacted for 1 hour with stirring, an opaque and non-uniform resin was obtained.

  Table 1 summarizes the properties of the aromatic polycarbonate copolymer resin and the chain-extended resin obtained in the examples.

  Table 1 shows the number of blocks expected when there is no exchange reaction in the carbonate bond, and the average number of blocks of the copolymers obtained in the examples (calculated from the NMR results). In any of the examples, it can be seen that the number of blocks is increased by the exchange reaction of the carbonate bond as compared with the case where there is no exchange reaction.

In addition, in the case of Example 1-1, in advance of an aromatic polycarbonate resin, although depolymerization bisphenol A, calculated molecular weight of depolymerized aromatic polycarbonate resin in this case was 2,500. From the results of NMR measurement, it was found that the block molecular weight of the aromatic polycarbonate resin component decreased from 2500 after the reaction with lactide. Usually, when an aromatic polycarbonate resin is depolymerized with a sufficient amount of bisphenol A, the number of terminal functional groups (in this case, phenolic hydroxyl groups) is two per one polycarbonate molecule produced by depolymerization. Also, a terminal functional group generated by copolymerization with a carbonate bond (in this case, the terminal generated by depolymerization with bisphenol A is composed of the same components as the original polycarbonate and does not contribute to copolymerization). If there is no exchange reaction, the polycarbonate block molecular weight of the compound obtained by copolymerization remains 2,500, and the number of blocks of the resulting copolymer is calculated to be 2.6 on average. However, in actuality, the block molecular weight decreased due to the exchange reaction, the number of blocks increased to 2.6 or more, and it can be seen that multi-blocking progressed.
From the above results, it was revealed that an aromatic polycarbonate copolymer resin composition in which an aromatic polycarbonate resin and a thermoplastic resin were chemically bonded via a carbonate bond was obtained by an exchange reaction.

  Further, the molecular weight of the added polycarbonate is 13,000. However, as the ester carbonate exchange reaction proceeds, the block molecular weight of the polycarbonate is considerably smaller than 13,000 in Table 1 as shown in Table 1. ing. The compound obtained by chain extension is considered to be a multi-block copolymer.

It is a proton NMR spectrum of the aromatic polycarbonate copolymer resin prepared in Example 1 -1. A carbon NMR spectrum of the aromatic polycarbonate copolymer resin prepared in Example 1 -1.

Claims (7)

In the method for producing an aromatic polycarbonate copolymer resin containing an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component, the thermoplastic resin (B) component is a polylactic acid resin, and an active hydrogen-containing functional group A method for producing an aromatic polycarbonate copolymer resin, comprising: reacting a compound (C) having a reaction with an aromatic polycarbonate resin (A), and then polymerizing a raw material compound (B ′) of a thermoplastic resin. In the method for producing an aromatic polycarbonate copolymer resin containing an aromatic polycarbonate resin (A) component and a thermoplastic resin (B) component, the thermoplastic resin (B) component is a polylactic acid resin, and an active hydrogen-containing functional group A method for producing an aromatic polycarbonate copolymer resin, comprising reacting a compound (C) having an aromatic group with an aromatic polycarbonate resin (A) and then reacting a thermoplastic resin (B). The method for producing an aromatic polycarbonate copolymer resin according to claim 1 or 2, wherein the functional group of the compound (C) having an active hydrogen-containing functional group is a hydroxyl group. The method for producing an aromatic polycarbonate copolymer resin according to any one of claims 1 to 3, wherein the reaction is performed in a molten state. Per 100 parts by mass of the obtained aromatic polycarbonate copolymer resin, it claims 1-4, characterized in that the reaction is carried out in the presence of a transesterification catalyst (D) 0.001 to 0.1 parts by weight A process for producing an aromatic polycarbonate copolymer resin as described in 1 above. The method for producing an aromatic polycarbonate copolymer resin according to any one of claims 1 to 5 , wherein a chain extension reaction is performed after the reaction. The aromatic polycarbonate copolymer resin obtained by the manufacturing method in any one of Claims 1-6 .