JP2011032433A - Method for preparing polycarbonate-polydiorganosiloxane copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a preparation method whereby a polycarbonate-polydiorganosiloxane copolymer can be efficiently obtained in an industrial scale, provided that the copolymer has a low oligomer content and a narrow molecular weight distribution. <P>SOLUTION: The method for preparing the polycarbonate-polydiorganosiloxane copolymer includes: previously preparing a mixed solution containing an oligomer having a terminal chloroformate group by reacting a dihydric phenol (I) and an ester-forming compound in a mixture of a water-insoluble organic solvent and an aqueous alkaline solution; and subsequently adding a hydroxyaryl-terminated polydiorganosiloxane (II) to the mixed solution so as to carry out interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a polycarbonate-polydiorganosiloxane copolymer. More specifically, a method for efficiently producing a polycarbonate-polydiorganosiloxane copolymer having a very low molecular weight distribution and a narrow molecular weight distribution, which causes a decrease in productivity and residence heat stability, with simple equipment. Is intended to provide.

  Polycarbonate is excellent in impact resistance and has a high heat distortion temperature and transparency, so it is widely used in the production of molded products. However, the use of general raw materials such as bisphenol A is not sufficient in terms of performance. Therefore, it is desired to develop a polycarbonate having higher performance as the application field expands. Therefore, in order to adapt to expanding applications, research has been conducted on copolymers by introducing various copolymer monomer units into general monomer raw materials such as bisphenol A (BPA). In research on these copolymers, polycarbonate-polydiorganosiloxane copolymers composed of BPA and polydiorganosiloxane comonomer are known to be superior in flame retardancy and low temperature impact resistance compared to BPA homopolycarbonate. Yes. Polycarbonate-polydiorganosiloxane copolymers are typically made by reacting a mixture of polydiorganosiloxane-containing bisphenols and dihydric phenols such as BPA with aqueous acid acceptors such as phosgene and aqueous sodium hydroxide under interfacial conditions. Is done.

  For example, in Patent Document 1, Patent Document 2, and Patent Document 3, polydiorganosiloxane-containing bisphenol is dissolved in a sodium hydroxide aqueous solution together with a dihydric phenol such as BPA, and a suspension solution in which methylene chloride is further added. A production method in which phosgene is introduced and reacted is disclosed. However, the polycarbonate-polydiorganosiloxane copolymer obtained by such a production method has a large molecular weight distribution due to a large amount of oligomer components, and the separation of the water phase and the organic phase during washing and washing is poor and the production efficiency is not only poor, This is not preferable because the residence heat stability deteriorates.

  In Patent Document 4, Patent Document 5, and Patent Document 6, a dihydric phenol such as BPA and phosgene are reacted in advance in a mixed solution of methylene chloride and an aqueous sodium hydroxide solution. Separate the phases, prepare a methylene chloride solution of chloroformate-terminated polycarbonate oligomer, add polydiorganosiloxane-containing bisphenol and a terminal terminator to this oligomer solution, add sodium hydroxide aqueous solution and methylene chloride, and then add triethylamine. A production method by carrying out a polycondensation reaction using as a catalyst is disclosed. However, in such a production method, in addition to the need for a step of allowing the reaction liquid to stand to separate the organic phase, it is necessary to add a sodium hydroxide aqueous solution to the separated organic phase. ineffective.

  In Patent Document 7, the pH is about 10 to about 12 under the interfacial reaction conditions consisting of an aqueous solvent and an organic solvent in the presence of an effective amount of a phase transfer catalyst as a catalyst for the reaction of a dihydric phenol and phosgene such as BPA. While maintaining the pH range, adding from about 1 to about 99 mol% phosgene based on the total number of moles of hydroxyl groups of the bisphenol, reducing the pH to the range of about 8-9, while maintaining such pH range The addition of phosgene to the mixture is continued at least in a sufficient amount and up to an excess of about 5 mole percent, the polydiorganosiloxane-containing bisphenol is introduced, and the pH is increased to a value in the range of about 10 to about 12. , A process for removing excess chloroformate groups is disclosed. In US Pat. No. 6,057,089, an aromatic bis compound is prepared by mixing a dihydric phenol such as BPA with phosgene, a phase transfer catalyst, an aqueous solvent and an organic solvent under interfacial reaction conditions while maintaining the pH at about 3 to about 8. After producing chloroformate and reacting this aromatic bischloroformate with polydiorganosiloxane-containing bisphenol, the pH is adjusted to a value of about 10 to about 14 so that the residual chloroformate remains at 50 ppm or less. Until the reaction is complete, and then an auxiliary such as a chain terminator, co-phosgenation catalyst, etc. is added to the resulting mixture, sufficient to complete the reaction while maintaining the pH in the range of about 9 to about 12. A process for adding phosgene is disclosed. However, in such a production method, it is necessary to frequently adjust the pH, and in some cases, phosgene must be introduced in a plurality of times, which complicates the production equipment and production process, resulting in poor production efficiency.

JP-A-3-79626 JP-A-4-202466 JP-A-5-247195 Japanese Patent No. 2662310 Japanese Patent Laid-Open No. 6-100654 JP-A-6-263865 JP-A-8-169947 JP 2006-518803 A

  The present invention solves the above-mentioned problems in the production of polycarbonate-polydiorganosiloxane copolymers found in the prior art, is an efficient method on an industrial scale, and is excellent in productivity and economy. Another object of the present invention is to provide a production method capable of obtaining a polycarbonate-polydiorganosiloxane copolymer having a narrow molecular weight distribution.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor preliminarily copolymerized an aromatic dioxy compound and a hydroxyaryl-terminated polydiorganosiloxane with an oligomer having a terminal chloroformate group of the aromatic dioxy compound in advance. Is then added to the mixed solution and subjected to interfacial polycondensation to produce a high molecular weight polycarbonate-polydiorganosiloxane copolymer with a small amount of oligomer components and a narrow molecular weight distribution on an industrial scale. And the present invention has been completed based on this finding. According to the present invention, the above problem is solved by the following configuration.

(Configuration 1)
A mixture containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (I) represented by the following general formula [1] and an ester-forming compound in a mixture of an organic solvent insoluble in water and an aqueous alkaline solution in advance. Next, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [3] is added to the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. A process for producing a polycarbonate-polydiorganosiloxane copolymer.

［上記一般式［１］において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数３〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式[２]で表される基からなる群より選ばれる少なくとも一つの基である。

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2].

（上記一般式［２］においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。）］

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

（上記一般式［３］において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは５００未満の自然数である。ＸはＣ_２〜Ｃ_８の二価脂肪族基である。）

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number in it, q is 0 or a natural number, p + q is a natural number less than 500 .X is a divalent aliphatic group of _C 2 _{~C 8.)}

(Configuration 2)
2. The method according to item 1, wherein the polycarbonate-polydiorganosiloxane copolymer has a molecular weight distribution (Mw / Mn) of 2.8 or less.
(Configuration 3)
2. The method according to item 1, wherein the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula [3] is (2-allylphenol) -terminated polydiorganosiloxane.
(Configuration 4)
2. The production method according to item 1, wherein the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula [3] is (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane.
(Configuration 5)
2. The production method according to item 1 above, wherein p + q is 5 to 70.
(Configuration 6)
2. The method according to item 1, wherein the polydiorganosiloxane block represented by the general formula [3] is 0.1 to 50 wt%.
(Configuration 7)
2. The production method according to item 1 above, wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are methyl groups.

  According to the method of the present invention, a polycarbonate-polydiorganosiloxane copolymer having a narrow molecular weight distribution can be obtained easily and stably. The polycarbonate-polydiorganosiloxane copolymer obtained by the method of the present invention is extremely useful as a material for general industrial materials and electrical / electronic equipment parts.

Details of the present invention will be described below.
Examples of the dihydric phenol (I) represented by the general formula [1] used in the production method of the present invention include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, and 1,1-bis. (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-) Methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy) Phenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) ) Propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9- Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Cyclopentane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy- , 3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyl Diphenol, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 2,2′-diphenyl-4,4′-sulfonyldiphenol 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4-hydro Cyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1, 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis { 2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4 Hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [3], for example, the following compounds are preferably used.

The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, 2-methoxy-4-allylphenol. It is easily produced by hydrosilation reaction at the end of a polysiloxane chain having a degree of polymerization. Of these, (2-allylphenol) -terminated polydiorganosiloxane and (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane, especially (2-methoxy-4) -Allylphenol) -terminated polydimethylsiloxane is preferred. A suitable polydiorganosiloxane polymerization degree (p + q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is 5 to 70. Such polydiorganosiloxane polymerization degree (p + q) is preferably 5 to 60, more preferably 5 to 40. If the amount is less than the lower limit of the preferable range, the impact resistance and flame retardancy are inferior. If the upper limit of the preferable range is exceeded, the amount of polydiorganosiloxane monomer introduced is significantly reduced with respect to the charged amount. The content of the polydiorganosiloxane component constituting the polycarbonate-polydiorganosiloxane copolymer is suitably 0.1 to 50 wt%. The polydiorganosiloxane component weight ratio is preferably 1 to 40 wt%, more preferably 1 to 20 wt%. If the amount is less than the lower limit of the preferable range, the impact resistance and flame retardancy are not sufficiently exhibited. If the upper limit of the preferable range is exceeded, the amount of polydiorganosiloxane monomer introduced is significantly reduced with respect to the charged amount. Such polydiorganosiloxane polymerization degree and polydiorganosiloxane component content can be calculated by ¹ H-NMR measurement.

In the method of the present invention, hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.
In addition, other comonomers other than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) can be used in combination as long as they do not interfere with the method of the present invention.

  In the method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (I) and a carbonate-forming compound in a mixed solution of an organic solvent insoluble in water and an aqueous alkaline solution in advance. To prepare.

In producing the oligomer of the dihydric phenol (I), the whole amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at one time, or a part of the dihydric phenol (I) is used as a post-added monomer at the subsequent interface. You may add to a polycondensation reaction as a reaction raw material. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.
Although the method of this oligomer production | generation reaction is not specifically limited, Usually, the method performed in the liquid mixture of water and the organic solvent insoluble in water in the presence of an acid binder is suitable.

  The use ratio of the carbonate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using gaseous carbonate ester-forming compounds, such as phosgene, the method of blowing this into a reaction system can be employ | adopted suitably.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.
The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, it is preferable to use 2 equivalents or slightly more acid binder than the number of moles of dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents). .

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The reaction pressure for oligomer formation is not particularly limited, and any of normal pressure, pressurization, and reduced pressure may be used, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
The pH range of the oligomer formation reaction is the same as the known interfacial reaction conditions, and the pH is always adjusted to 10 or more.

  In the present invention, after obtaining a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group in this way, hydroxyaryl-terminated polydiorganosiloxane (II) is added to the mixed solution, A polycarbonate-polydiorganosiloxane copolymer is obtained by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

  In performing the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalent) of the reaction. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) to be used or a part of the dihydric phenol (I) as described above is added as a post-added monomer to this reaction stage, It is preferable to use 2 equivalents or an excess amount of alkali with respect to the total number of moles of monovalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

  The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

  In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monohydric phenolic hydroxyl group. In addition to ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., long-chain alkylphenols, aliphatic carboxylic acids Examples include chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxyphenylalkyl acid ester, alkyl ether phenol and the like. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, based on 100 mol of all dihydric phenol compounds used, and it is naturally possible to use two or more compounds in combination. is there.

In order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.
If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.
The method of the present invention can be continued without departing from the spirit of the present invention.

  A branching agent can be used in combination with the above dihydric phenol compound to form a branched polycarbonate. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

The ratio of the polyfunctional compound in the branched polycarbonate resin is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, more preferably 0.01 to 0.8 mol in the total amount of the aromatic polycarbonate resin. The mol%, particularly preferably 0.05 to 0.4 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also preferably in the above-mentioned range in the total amount of the aromatic polycarbonate resin. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

The reaction pressure can be any of reduced pressure, normal pressure, and increased pressure. Usually, it can be suitably carried out at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.
The pH range of the interfacial polycondensation reaction is the same as known interfacial polycondensation reaction conditions, and the pH is always adjusted to 10 or more.

  The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer is suitably in the range of 10,000 to 50,000. The viscosity average molecular weight is preferably 13,000 to 30000, more preferably 15000 to 25000. When the viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer is less than 10,000, practical mechanical strength is difficult to obtain in many fields, and when it exceeds 50,000, the melt viscosity is high and generally a high molding processing temperature is required. To do.

The viscosity average molecular weight referred to in the present invention is obtained by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate resin is dissolved in 100 ml of methylene chloride at 20 ° C., the specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.

  The obtained reaction product (crude product) is separated into an aqueous phase composed of unreacted aromatic dihydroxy compounds and by-product chlorides, carbonates and caustics, and an organic phase composed of an organic solvent solution of polycarbonate resin. To do. When the separation is insufficient, the separation is performed using a means such as stationary separation or centrifugation. Usually, the polycarbonate resin solution after the polymerization reaction is obtained as a concentration of 4 to 27 w / w%, but it is preferable to dilute it in advance to 19 w / w% or less in order to improve the separability. The separated organic phase is extracted with an acidic aqueous solution such as an aqueous hydrochloric acid solution, if necessary, to extract and remove basic components (eg, organic amines) in the polycarbonate resin solution, or sodium hydroxide. An aqueous alkaline solution such as an aqueous solution can be used to extract and remove dihydroxy compounds that are unreacted monomers in the polycarbonate resin solution. Impurities are removed by washing the separated organic phase with water. The water used in this step has an electrical conductivity of preferably 50 μS / cm or less, more preferably 10 μS / cm or less, and even more preferably 1 μS / cm or less. Specifically, it is purified water, such as distilled water or ion exchange water. The washing operation with water is carried out by mixing and stirring the polycarbonate resin solution and water, separating the organic phase and the aqueous phase, and taking out the organic phase.

  The water washing in this step is performed at least once, preferably 1 to 3 times, more preferably 1 to 2 times. The number of water washings varies depending on the purity and amount of water used. Usually, the amount of water used at one time is in the range of 5 to 200 parts by volume, preferably 10 to 100 parts by volume per 100 parts by volume of the polycarbonate resin solution.

  Here, if the separation between the water phase and the organic phase is poor and a clear interface is not formed in the water washing step, the production efficiency is remarkably reduced, so the separation between the water phase and the organic phase in the water washing step is good and clear. It is preferred that an interface be formed.

  The separated and purified resin solution can be granulated by a conventional method such as dropping it into hot water under stirring or putting it into a kneader. By drying a polycarbonate resin granular material containing a solvent and moisture with a dryer, a granular material suitable for extrusion or molding can be obtained.

  The following examples further illustrate the present invention. In addition, the part in an Example is a weight part and% is weight%. The evaluation was performed according to the following method.

(1) Viscosity average molecular weight (Mv)
Using a Ostwald viscometer, a specific viscosity (η _SP ) calculated by the following formula was determined from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η]2c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(2) Molecular weight distribution (Mw / Mn)
The polystyrene conversion measurement by gel permeation column chromatography method (GPC method) was implemented using HLC-8220GPC manufactured by Tosoh Corporation. Three columns with an inner diameter of 4.6 cm and a length of 15 cm packed with TSK-gelSuperHZ4000, 3000, and 2000, respectively, were used as the packing material. Chloroform was flowed at a rate of 0.35 ml / min as a moving bed at 40 ° C. Detection was by ultraviolet light.

Example 1
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 21592 parts of ion-exchanged water and 3675 parts of 48.5% aqueous sodium hydroxide solution were added, and 2 as dihydric phenol (I) represented by the general formula [1]. After dissolving 3897 parts of 2-bis (4-hydroxyphenyl) propane (bisphenol A) and 7.6 parts of hydrosulfite, 14565 parts of methylene chloride are added, and 1900 parts of phosgene are added for 60 minutes at 22-30 ° C. with stirring. In short, I blew in. A solution obtained by dissolving 1131 parts of 48.5% aqueous sodium hydroxide solution and 108 parts by weight of p-tert-butylphenol in 800 parts of methylene chloride was added and stirred as a dihydric phenol (II) represented by the general formula [3]. A solution prepared by dissolving 205 parts by weight of a polydiorganosiloxane compound (X-22-1821, manufactured by Shin-Etsu Chemical Co., Ltd.) in 800 parts of methylene chloride was added to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts by weight of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued at a temperature of 26 to 31 ° C. for 1 hour to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. The methylene chloride was evaporated while stirring to obtain a polycarbonate-polydimethylsiloxane copolymer powder. The copolymer had a viscosity average molecular weight of 19,600 and Mw / Mn was 2.35. In the washing and washing, a clear interface was formed in a short time, and the separation property between the organic phase and the aqueous phase was extremely good. The results are shown in Table 1.

Example 2
The procedure was the same as Example 1 except that 3880 parts of 2,2-bis (4-hydroxyphenyl) propane and 430 parts by weight of dihydric phenol (II) represented by the general formula [3] were used. The viscosity average molecular weight of this copolymer was 20,100, and Mw / Mn was 2.52. The results are also shown in Table 1.

Example 3
The procedure was the same as Example 1 except that 3860 parts of 2,2-bis (4-hydroxyphenyl) propane and 681 parts by weight of dihydric phenol (II) represented by the general formula [3] were used. The copolymer had a viscosity average molecular weight of 20,000 and Mw / Mn of 2.59. Separation between the organic phase and the aqueous phase was very good in washing with water, and a clear interface was formed in a short time. The results are also shown in Table 1.

Example 4
As a dihydric phenol (II) represented by general formula [3] with 3889 parts of 2,2-bis (4-hydroxyphenyl) propane, a polydiorganosiloxane compound having the following structure (Shin-Etsu Chemical Co., Ltd. X- 22-1875) was used in the same manner as in Example 1 except that 205 parts by weight was used. The viscosity average molecular weight of this copolymer was 19,100, and Mw / Mn was 2.44. Separation between the organic phase and the aqueous phase was very good in washing with water, and a clear interface was formed in a short time. The results are also shown in Table 1.

Example 5
The same procedure as in Example 4 was repeated, except that 3867 parts of 2,2-bis (4-hydroxyphenyl) propane and 429 parts by weight of dihydric phenol (II) represented by the general formula [3] were used. This copolymer had a viscosity average molecular weight of 18,700 and Mw / Mn of 2.57. Separation between the organic phase and the aqueous phase was very good in washing with water, and a clear interface was formed in a short time. The results are also shown in Table 1.

Example 6
The same procedure as in Example 4 was repeated, except that 3840 parts of 2,2-bis (4-hydroxyphenyl) propane and 678 parts by weight of dihydric phenol (II) represented by the general formula [3] were used. The copolymer had a viscosity average molecular weight of 18,600 and Mw / Mn was 2.53. Separation between the organic phase and the aqueous phase was very good in washing with water, and a clear interface was formed in a short time. The results are also shown in Table 1.

Comparative Example 1
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 21592 parts of ion-exchanged water and 3675 parts of 48.5% aqueous sodium hydroxide solution were added, and 2 as dihydric phenol (I) represented by the general formula [1]. 3897 parts of 2-bis (4-hydroxyphenyl) propane (bisphenol A) and the above polydiorganosiloxane compound (X-22- manufactured by Shin-Etsu Chemical Co., Ltd.) as the dihydric phenol (II) represented by the general formula [3] 1821) After dissolving 205 parts by weight and 7.6 parts of hydrosulfite, 14565 parts of methylene chloride was added, and 1900 parts of phosgene was blown in at a temperature of 22-30 ° C. for 60 minutes with stirring. A solution prepared by dissolving 1131 parts of a 48.5% aqueous sodium hydroxide solution and 108 parts by weight of p-tert-butylphenol in 800 parts of methylene chloride was added to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts by weight of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued at a temperature of 26 to 31 ° C. for 1 hour to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. The methylene chloride was evaporated while stirring to obtain a polycarbonate-polydimethylsiloxane copolymer powder. The copolymer had a viscosity average molecular weight of 21,200 and Mw / Mn of 3.16. It took a long time to form a clear interface in washing and washing, and the separability between the organic phase and the aqueous phase was poor. The results are also shown in Table 1.

  The polycarbonate-polydiorganosiloxane copolymer obtained in the present invention includes various optical disks such as optical disks and related members, various housing molded products such as battery housings, lens barrels, memory cards, speaker cones, disk cartridges, surface light emitters, It is extremely useful because it can be widely used in micromachine mechanism parts, hinged molded articles or hinge molded parts, optical parts such as translucent / light-guiding buttons, touch panel parts, electrical / electronic devices, and automobiles. .

Claims (7)

A mixture containing an oligomer having a terminal chloroformate group by the reaction of a dihydric phenol (I) represented by the following general formula [1] and an ester-forming compound in a mixture of an organic solvent insoluble in water and an aqueous alkaline solution in advance. Next, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [3] is added to the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation. A process for producing a polycarbonate-polydiorganosiloxane copolymer.

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2].

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7).

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number in it, q is 0 or a natural number, p + q is a natural number less than 500 .X is a divalent aliphatic group of _C 2 _{~C 8.)}   The manufacturing method of Claim 1 whose molecular weight distribution (Mw / Mn) of a polycarbonate polydiorganosiloxane copolymer is 2.8 or less.   The production method according to claim 1, wherein the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula [3] is (2-allylphenol) -terminated polydiorganosiloxane.   The production method according to claim 1, wherein the hydroxyaryl-terminated polydiorganosiloxane represented by the general formula [3] is (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane.   The manufacturing method of Claim 1 whose p + q is 5-70.   The manufacturing method of Claim 1 whose polydiorganosiloxane block represented by General formula [3] is 0.1-50 wt%. The manufacturing method of Claim 1 whose R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ >, R <^7> , R < ⁸ > is a methyl group.