JPH0822927B2 - Method for producing polystyrene-polycarbonate block copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel method for producing a polystyrene-polycarbonate block copolymer.

2. Description of the Related Art Conventionally, there is the following method for producing a polystyrene-polycarbonate block copolymer using a styrene-based polymer having a reactive functional group at the terminal and a polycarbonate having a hydroxyl group at the terminal.

First, bisphenol A and phosgene are subjected to interfacial polycondensation in the presence of excess alkali to obtain a polycarbonate having a hydroxyl group at the terminal. Then, polystyrene is synthesized by radically polymerizing styrene with benzoyl peroxide as an initiator, and the initiator residue at the terminal of this polystyrene is hydrolyzed to obtain polystyrene having hydroxyl groups. Then, the polystyrene having a hydroxyl group end is reacted with phosgene to form a chloroformate at the end of the polystyrene, and then a polycarbonate having a hydroxyl group at the end is reacted (SHMerril
l, Journal of Polymer Science, vol.55, pages 343 ~ 3
52 (1962)). Since phosgene is used in the above method, there are the following problems.

(1) Since phosgene is highly toxic, care must be taken when handling it, including measures for equipment.

(2) It is difficult to obtain raw materials for phosgene because it is legally restricted to move or carry it out.

(3) A purification step by washing is necessary in order to prevent the phosgene, the chloroformate end, and the alkaline component in the produced polymer from remaining.

As described above, the conventionally known technique has problems in industrial manufacturing such as an increase in process and cost as well as safety.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the above-mentioned problems of the prior art using phosgene, and enables polystyrene-polycarbonate block copolymers to be synthesized easily and efficiently.
The purpose of the present invention is to provide a manufacturing method advantageous for industrial implementation.

Therefore, the present inventors considered the following points in order to solve such a problem.

(1) Do not use phosgene, which has the problems of safety and increase in process and cost.

(2) To use the polymerization technique of each homopolymer as it is to control the molecular weight and molecular weight distribution of each homopolymer chain in the block copolymer and the composition of the block copolymer.

(3) In order to avoid an increase in costs associated with an increase in the number of steps, the polymer is directly condensed without going through a process such as acid chloride formation.

Means for Solving the Problems That is, in the present invention, in obtaining a polystyrene-polycarbonate block copolymer, a styrene polymer having a carboxyl group terminal and a polycarbonate having a hydroxyl group terminal are reacted with a phosphine compound and a phosphine compound. In the presence of a halogen or a halide forming a phosphonium salt, an acid scavenger and a solvent.

 This will be described in detail below.

The styrene-based polymer having a carboxyl group terminal used in the present invention is not particularly limited as long as it has a carboxyl group terminal at the molecular chain terminal, and may be appropriately determined depending on the use of the copolymer to be produced and the like. .

Here, the styrene polymer used in the present invention can be synthesized, for example, by the following method. That is, JP-B-43-11224 and JP-A-60-133.
007, JP 61-64705, Advances in Poly
As disclosed in mer Science Vol.62, 95 (1984) and the like, a radical polymerizable monomer such as styrene is polymerized in the presence of a radical polymerization initiator having a carboxyl group or a chain transfer agent having a carboxyl group, A styrene-based polymer having a carboxyl group terminal can be obtained.

Also. U.S. Pat.Nos. 4,085,168, 3,928,255, 3,
As disclosed in 862,267 and 3,786,116, the target styrene-based polymer can be obtained by reacting a living polymer anion such as styrene with maleic anhydride or the like.

Further, as a commercial product, a styrene-acrylonitrile copolymer having a dicarboxylic acid at one end (trade name: Aron macromonomer MDC-5AS, manufactured by Toagosei Kagaku Kogyo Co., Ltd.) and the like can be used. The main skeleton in the styrene-based polymer having a carboxyl group terminal is selected in consideration of the use of the block copolymer to be produced, and preferred examples thereof include polystyrene and poly-
p-methylstyrene, poly-α-methylstyrene, poly-m-methoxystyrene, poly-p-methoxystyrene, acrylonitrile-styrene copolymer, styrene-
Butadiene block copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-butadiene copolymer, styrene-p-methylstyrene copolymer, styrene-α-methylstyrene copolymer, styrene-m-methoxystyrene copolymer Coalesce, styrene-p-methoxystyrene copolymer, methyl methacrylate-styrene copolymer,
Examples thereof include ethyl methacrylate-styrene copolymer, butyl methacrylate-styrene copolymer, methyl acrylate-styrene copolymer, ethyl acrylate-styrene copolymer, butyl acrylate-styrene copolymer and the like.

Next, the polycarbonate used in the present invention is one having a hydroxyl group at the terminal, but the polycarbonate having a hydroxyl group end has a diphenol compound and phosgene in the presence of an alkali, as disclosed in the aforementioned document of SH Merrill et al. It can be obtained by interfacial polycondensation below. Alternatively, Belgian Patent No. 675,190, and No. 6
It is obtained by melt polycondensation of a diphenol compound and diphenyl carbonate, as disclosed in 77,424.

Further, a commercially available polycarbonate may be appropriately hydrolyzed to obtain a polycarbonate having a hydroxyl group at the terminal.

The main skeleton of the polycarbonate having a hydroxyl group terminal used in the present invention should be selected in consideration of the application of the block copolymer to be produced, etc., but as described above, the polycarbonate having a hydroxyl group terminal has various types. It is obtained by reacting a diphenol compound with phosgene or diphenyl carbonate. Therefore, the main skeleton of the polycarbonate is largely controlled by the selection of the diphenol compound.

The diphenol compounds that can be selected as the main skeleton of the polycarbonate used in the present invention are as follows. 2,2-bis (4-hydroxyphenyl) propane, 2,4'-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) Methane, bis (4-hydroxy-2,6
-Dimethyl-3-methoxyphenyl) methane, 1,1-
Bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4
-Hydroxy-2-chlorophenyl) ethane, 1,1-
Bis (2,5-dimethyl-4-hydroxyphenyl) ethane, 1,3-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2
-Bis (4-hydroxynaphthyl) propane, 2,2-
Bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) heptane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxy) Phenyl) cyclohexylmethane, 1,2-bis (4
-Hydroxyphenyl) -1,2-bis (phenyl) ethane, 2,2-bis (4-hydroxyphenyl) -1,
3-bis (phenyl) propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 4,4 '
-Dihydroxy-diphenyl, 2,2'-dihydroxyphenyl, 2,4'-dihydroxydiphenyl, 2,6
-Dihydroxynaphthalene, bis (p-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, 5'-chloro-2-4'-dihydroxydiphenyl sulfone, 3'-chloro-4-4'-dihydroxydiphenyl sulfone, p, p'-dihydroxydiphenyl ether, p, p'-dihydroxytriphenyl ether, 4,3 '-, 4,2'-4,1'-, 2,2 '
-2,3'-, etc. dihydroxydiphenyl ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, 4,4'-dihydroxy-2,5-dimethyldiphenyl ether, 4,4'-dihydroxy-
3,3'-diisobutyldiphenyl ether and the like. These diphenol compounds can be used not only alone but also as a mixture for the synthesis of polycarbonate having a hydroxyl group end.

Further, the main skeleton of the polycarbonate having a hydroxyl group terminal used in the present invention is a dihydroxybenzene compound,
An aliphatic dihydroxy compound, an aliphatic dicarboxylic acid compound, an aliphatic-aromatic dicarboxylic acid compound, an aromatic dicarboxylic acid compound, and a compound obtained by partially copolymerizing various hydroxycarboxylic acid compounds can also be used.

Next, as the phosphine compound used in the present invention, triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-methoxyphenyl) phosphine, tris (2-methoxyphenyl) phosphine, tris (2,6- Dimethoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, (2-methoxyphenyl) diphenylphosphine, (2,6-dimethoxyphenyl) diphenylphosphine, trimethylphosphine, triethylphosphine,
Tri-n-propylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-tert
-Butylphosphine, trioctylphosphine, trinonylphosphine, tribenzylphosphine, tritolylphosphine, tricyclohexylphosphine, ethyldimethylphosphine, α-naphthyldiphenylphosphine, p-tolyldiphenylphosphine, vinyldiphenylphosphine, methyldiphenylphosphine, ethyldiphenyl Phosphine, dimethylphenylphosphine, diethylphenylphosphine, dibenzylphenylphosphine, dimethylcyclohexylphosphine, tris-
(Cyanoethyl) phosphine, hexaethylphosphorus triamide, etc. and mixtures of these compounds.

Further, as the halogen or halide which reacts with the phosphine compound used in the present invention to form a phosphonium salt, carbon tetrachloride, chloroform, methylene chloride,
1,2-dichloroethane, 1,1-dichloroethane,
1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, hexachloroethane, trichloroethylene, hexachloroacetone, carbon tetrabromide, carbon tribromide, hexabromoethane, Examples include chlorine, bromine, iodine and the like and mixtures thereof.

Examples of the acid scavenger used in the present invention include triethylamine, diethylamine, N-methylmorpholine, pyridine, 2-pcholine, 3-picoline, 4-picoline,
2,4-lutidine, 2,6-lutidine, 3,5-lutidine, quinoline and the like, and mixtures of these acid scavengers.

According to the method of the present invention, a carboxyl group of a styrenic polymer having a carboxyl group end is activated by a phosphonium salt formed from a phosphine compound and a halogen or a halide, and is reacted with a polycarbonate having a hydroxyl end in the presence of an acid scavenger. It is a thing. In the reaction, a solution polymerization method using a solvent is usually used. The solvent can be used by using an excess amount of a halide. Further, each of the raw material components used in the present invention and those which do not substantially react with the intermediate phosphonium salt, and a good solvent for the raw material components, further, the reaction product polystyrene-polycarbonate block It is desirable that the solvent is a good solvent for the copolymer. Examples of such a solvent include dichloromethane, chloroform, 1,2-dichloroethane, 1,2-dichloroethylene, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, tetrahydrofuran, 1,4-dioxane, There are thiophene, acetophenone, anisole, benzonitrile, cyclohexanone, dimethylformamide, nitrogensenzen, etc. and mixtures thereof.

The block copolymer can be produced by the method of the present invention by appropriately selecting, for example, the following procedure.

(1) A phosphine compound and a halogen or a halide which reacts with the phosphine compound to form a phosphonium salt are charged into a reaction vessel, and then a styrene polymer having a carboxyl group end is charged. Then, a polycarbonate having a hydroxyl group end and an acid scavenger are added.

(2) Phosphine compounds, halogens or halides that react with phosphine compounds to form phosphonium salts,
A styrene-based polymer having a carboxyl group end is simultaneously added to a reaction vessel, and then a hydroxyl group-terminated polycarbonate and an acid scavenger are charged.

(3) Phosphine compounds, halogens or halides that react with phosphine compounds to form phosphonium salts,
A styrene-based polymer having a carboxyl group terminal, a polycarbonate having a hydroxyl group terminal, and an acid scavenger are simultaneously charged into a reactor.

In order to charge each raw material component into the reaction vessel, each component may be dissolved in the appropriate solvent in advance and then charged into the reactor, or a part or all of each raw material component may be in a solid state. It may be charged into a reactor filled with the solvent or solution.
Alternatively, a part of the raw material components may be charged in a gaseous state by blowing into the reactor. Further, these methods may be combined and charged. In the method of the present invention, it is desirable to adjust the amount of solvent in the reactor so that the total concentration of the raw material components in the solution is 1 to 40% by weight, preferably 3 to 30% by weight.

On the other hand, the charging amount of the styrene-based polymer having a carboxyl group terminal and the polycarbonate having a hydroxyl group terminal is such that the total amount of terminal carboxyl groups in the styrene-based polymer and the total amount of terminal hydroxyl groups in the polycarbonate-based polymer become distant from each other. Is most desirable for increasing the molecular weight of the resulting block copolymer.

Here, the total amount of carboxyl groups can be determined by neutralizing and titrating the polymer solution with an aqueous potassium hydroxide solution using phenolphthalein as an indicator. The total amount of hydroxyl groups was determined by trimethylsilylation of the terminal hydroxyl groups with trimethylsilyl chloride, followed by ¹ H-NMR.
It can be determined by the method of quantification in.

Further, the phosphine compound used in the present invention and the halogen or halide which reacts with this to form a phosphonium salt are equimolar amounts or more with respect to the total molar amount of the carboxyl groups of the styrene-based polymer having a carboxyl group terminal, preferably It is preferable to use an equimolar amount or more and a 10-fold molar amount or less.

Furthermore, the amount of the acid scavenger to be used needs to be an equimolar amount or more with respect to the total amount of carboxyl groups contained in the polystyrene-based polymer having a carboxyl group terminal.
It is preferably used in an equimolar amount to 20 times the molar amount.

Further, the synthesis reaction conditions of the polystyrene-polycarbonate block copolymer according to the present invention, the styrene polymer having a carboxyl group end to be used, and the type, molecular weight, concentration of the polycarbonate having a hydroxyl end,
Further, it is appropriately selected and set depending on the kind of phosphine compound, halide, or halogen, acid scavenger, solvent used, amount used, etc.
It is carried out with stirring in the range of to 200 ° C, preferably 10 to 150 ° C.
The reaction is usually carried out under normal pressure, but it may be carried out under reduced pressure or under increased pressure. The reaction time is 1 minute to 24 hours, preferably 3 minutes to 10 hours.

The reaction for producing the polystyrene-polycarbonate block copolymer according to the present invention is carried out by activating the carboxyl group introduced at the terminal of the styrene polymer with a phosphine compound and a halide or a phosphonium salt generated from halogen, and having a hydroxyl group terminal. It is to be reacted with polycarbonate.

The block copolymer is produced by the reaction between the terminal groups of each polymer, and therefore, the polymerization of the same polymer is hardly caused, and the degree of polymerization of each polymer is maintained almost unchanged even in the copolymer. Therefore, since the composition of the obtained block copolymer is determined by each polymer used, the composition and degree of polymerization of the block copolymer can be freely controlled. In addition, according to the present invention, a polystyrene-polycarbonate-based block copolymer can be obtained without using phosgene, so that various problems such as safety and process and cost increase associated with the use of phosgene can be avoided. You can Further, according to the present invention, each polymer is directly condensed without undergoing a process such as acid chloride conversion of the terminal carboxylic acid of the polymer, so that an increase in cost due to an increase in the number of steps can be avoided.

Further, since the block copolymer obtained by the present invention has high moldability and high transparency, it can be used not only in electric products, machine parts, daily sundries, etc., but also in adhesives, paints, molded products, resins. It is extremely useful for modifying asphalt, asphalt, and blends of different polymers.

EXAMPLES The method of the present invention will be described in more detail with reference to the following examples. The characteristic values of the styrene-based polymer having a carboxyl group terminal and the polycarbonate having a hydroxyl group terminal used in Examples 1 to 4 are as shown in Table 1. However, the weight average molecular weight (M _W ) and the number average molecular weight (M _N ) in Table 1 were measured using a 802A gel permeation chromatograph manufactured by Toyo Soda Co., Ltd. using monodisperse polystyrene as a standard sample. is there.

Example 1 A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, N ₂ gas and a raw polymer solution charging port was charged with triphenyl-.
A solution of 2.21 g (8.44 mmol) of phosphine in 50 ml of 1,2-dichloroethane is added. Next, a solution prepared by dissolving 2.36 g (9.97 mmol) of hexachloroethane in 50 ml of 1,2-dichloroethane was dropped from the dropping funnel. After completion of dropping, the mixture is stirred at room temperature for 20 minutes.

And an initiator having a carboxyl group, a styrene polymer-1 having a carboxyl group end obtained by radically polymerizing styrene in the presence of a chain transfer agent,
A solution of 25.00 g in 360 ml of 1,2-dichloroethane was added to the reactor. Then, the mixture was heated and refluxed for 20 minutes using an oil bath. After removing the oil bath and allowing it to cool for 10 minutes, 11.11 g of a polycarbonate-1 having a hydroxyl group terminal obtained by hydrolyzing a polycarbonate (Upilon S-1000 manufactured by Mitsubishi Gas Chemical Co., Inc.) in 260 ml of 1, 2 -Add the solution dissolved in dichloroethane and 1.6 ml of triethylamine, and then again with an oil bath.
The mixture was heated under reflux for 0 minutes.

After the reaction solution was cooled to room temperature, it was poured into methanol 3 for precipitation purification. Then, the polymer was separated by filtration and washed, and 1m
Degassing was performed at mHg and 70 ° C. to remove evaporated components. The weight of the obtained polymer was 35.46 g (yield; 98% by weight).

The obtained polymer was analyzed by gel permeation chromatography (GPC) and the polystyrene-equivalent weight average molecular weight (M
_W ) and number average molecular weight (M _N ) were measured. The results were 27,000 (M _W ) and 13000 (M _N ) respectively.

Further, as can be seen from the GPC chart shown in FIG. 1, the peak of the polymer of this example is shifted to the high molecular weight side as a whole with respect to the peak of the polymer, and a block copolymer is formed. Was confirmed.

Example 2 A solution of 5.73 g (21.86 mmol) of triphenylphosphine in 200 ml of 1,2-dichloroethane is placed in a reactor. Next, a solution prepared by dissolving 6.12 g (25.83 mmol) of hexachloroethane in 200 ml of 1,2-dichloroethane was added to the reactor and stirred at room temperature for 30 minutes.

And an initiator having a carboxyl group, a styrene polymer-2 having a carboxyl group end obtained by radically polymerizing styrene in the presence of a chain transfer agent,
A solution of 96.64 g in 1550 ml of 1,2-dichloroethane was added to the reactor. Then, the mixture was heated under reflux for 30 minutes.

Then, a solution prepared by dissolving 50.00 g of polycarbonate-2 having hydroxyl end groups obtained by melt polycondensation of bisphenol-A and diphenyl carbonate in 1000 ml of 1,2-dichloroethane and 4.1 ml of triethylamine are added to the reactor. . Then, the mixture was heated and refluxed again for 20 minutes.

The reaction solution was allowed to cool to room temperature and then poured into methanol 12 for precipitation purification. Then, the polymer was separated by filtration and washed, and 1m
It was devolatilized at mHg and 70 ° C. to remove the evaporated component. The weight of the obtained polymer was 144.8 g (yield; 99% by weight).

The polystyrene-equivalent weight average molecular weight (M _W ) and number average molecular weight (M _N ) of the polymer of this example measured by GPC were 52000 (M _W ) and 25000 (M _N ), respectively.

Further, as can be seen from the GPC chart shown in FIG. 2, the peak of the block copolymer was entirely shifted to the high molecular weight side with respect to the peak of the polymer.

Example 3 3.22 g (12.27 mmol) of triphenylphenyl was added to 1,
A solution of 50 ml 2-dichloroethane is placed in the reactor. Then hexachloroethane 3.43 g (14.50 mmol)
Was dissolved in 50 ml of 1,2-dichloroethane and added to the reactor, and the mixture was stirred at room temperature for 25 minutes.

And an initiator having a carboxyl group, a styrene polymer-3 having a carboxyl group end obtained by radically polymerizing styrene in the presence of a chain transfer agent,
A solution of 48.37 g in 806 ml of 1,2-dichloroethane was added to the reactor. Then, the mixture was heated under reflux for 20 minutes.

Then, a solution prepared by dissolving 40.95 g of a hydroxyl group-terminated polycarbonate-3 obtained by melt polycondensation of bisphenol-A and diphenyl carbonate in 880 ml of 1,2-dichloroethane and 2.3 ml of triethylamine are added to a reactor. . Then, the mixture was heated and refluxed again for 30 minutes.

The reaction solution was allowed to cool to room temperature and then poured into methanol 7.2 for precipitation purification. Then, the polymer was filtered and washed,
It was devolatilized at 1 mmHg and 70 ° C. to remove the evaporated component. The weight of the obtained polymer was 87.7 g (yield; 98% by weight).

The polystyrene-equivalent weight average molecular weight (M _W ) and number average molecular weight (M _N ) of the polymer of this example measured by GPC were 77,000 (M _W ) and 38000 (M _N ), respectively.

Further, as can be seen from the GPC chart shown in FIG. 3, the peak of the block copolymer was entirely shifted to the high molecular weight side with respect to the peak of the polymer.

Example 4 A solution of 0.76 g (2.90 mmol) of triphenylphosphine in 30 ml of 1,2-dichloroethane is placed in a reactor. Next, a solution prepared by dissolving 0.81 g (3.41 mmol) of hexachloroethane in 30 ml of 1,2-dichloroethane was added to the reactor and stirred at room temperature for 10 minutes.

And an initiator having a carboxyl group, a styrene polymer-4 having a carboxyl group end obtained by radically polymerizing styrene in the presence of a chain transfer agent,
A solution of 20.71 g in 354 ml of 1,2-dichloroethane was added to the reactor. Then, the mixture was heated under reflux for 20 minutes.

Then, 17.00 g of a hydroxyl group-terminated polycarbonate-4 obtained by melt polycondensation of bisphenol-A and diphenyl carbonate was dissolved in 340 ml of 1,2-dichloroethane, and 0.6 ml of triethylamine was added to the reactor. . Then, the mixture was heated and refluxed again for 25 minutes.

The reaction solution was allowed to cool to room temperature and then poured into methanol 3 for precipitation purification. Then, the polymer was separated by filtration, washed, and devolatilized at 1 mmHg and 70 ° C. to remove the evaporated component. The weight of the obtained polymer was 37.5 g (yield; 99% by weight).

The polystyrene-equivalent weight average molecular weight (M _W ) and number average molecular weight (M _N ) of the polymer of this example measured by GPC were 93000 (M _W ) and 39000 (M _N ), respectively.

Further, as can be seen from the GPC chart shown in FIG. 4, the peak of the block copolymer was entirely shifted to the polymer side with respect to the peak of the polymer.

EFFECTS OF THE INVENTION The method of the present invention forms a phosphonium salt by reacting a styrene-based polymer having a carboxyl group end and a polycarbonate having a hydroxyl group end with a phosphine compound and a phosphine compound to obtain a polystyrene-polycarbonate block copolymer. The reaction is carried out in the presence of a halogen or a halide, an acid scavenger and a solvent.

According to the method of the present invention, a polystyrene-polycarbonate block copolymer can be obtained without using phosgene, which is a drawback of the conventional method.

Moreover, since the method of the present invention is a reaction between end groups of a polymer having a specific functional group, the composition of the resulting block copolymer and the molecular weight of the raw polymer chain are determined by the raw polymer used. A polystyrene-polycarbonate block copolymer having a desired composition and molecular weight can be easily obtained with high precision.

Further, in the method of the present invention, each polymer is directly condensed without passing through the process of acid chloride conversion of the terminal carboxylic acid of the polymer, so that the number of steps can be avoided.

Furthermore, according to the method of the present invention in which a phosphine compound and a halide are used as a condensing agent, high temperature is not required during polycondensation, and the reaction is completed in a short time, so that decomposition of the polymer chain can be avoided. It also has the advantage.

Further, since the block copolymer obtained by the present invention has high moldability and high transparency, it can be used not only in electric products, machine parts, daily sundries, etc., but also in adhesives, paints, molded products, resins. It is extremely useful for modifying asphalt, asphalt, and blends of different polymers.

[Brief description of drawings]

FIGS. 1 to 4 are graphs showing the results of GPC measurement. The solid line shows the block copolymer, the one-dot chain line shows polystyrene having a carboxyl group terminal, and the dotted line shows polycarbonate having a hydroxyl group terminal.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroharu Inoue 1618 Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Nippon Steel & Co., Ltd. Technical Research Laboratories No. 1 (56) Reference JP-A-61-19656 A) JP 6119630 (JP, A)

Claims (1)

[Claims] 1. A styrene-based polymer having a carboxyl group terminal and a polycarbonate having a hydroxyl group terminal are present in the presence of a phosphine compound and a halogen or a halide forming a phosphonium salt, and an acid scavenger. A method for producing a polystyrene-polycarbonate block copolymer, which comprises reacting in a solution state in the presence of a solvent.