KR20170060564A - Polyethersulfon-polycarbonate copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to a thermoplastic copolymer resin having excellent heat resistance and transparency and a method for producing the same. More specifically, the present invention relates to a thermoplastic copolymer resin obtained by copolymerizing a polyarylene ether sulfonic oligomer having a specific structure with a polycarbonate oligomer, Transparency and fluidity, a method for producing the same, and a molded article comprising the same.

Description

TECHNICAL FIELD The present invention relates to a polyethersulfone-polycarbonate copolymer and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a thermoplastic copolymer resin having excellent heat resistance and transparency and a method for producing the same. More specifically, the present invention relates to a thermoplastic copolymer resin obtained by copolymerizing a polyarylene ether sulfonic oligomer having a specific structure with a polycarbonate oligomer, Transparency and fluidity, a method for producing the same, and a molded article comprising the same.

Polycarbonate resins are widely used as electrical parts, machine parts and industrial resins because of their excellent heat resistance, mechanical properties (particularly impact strength) and transparency. Particularly, when a polycarbonate resin is used for a TV housing, a computer monitor housing, a copying machine, a printer, a notebook battery, and a case material for a lithium battery, which are highly heat-dissipated in the electric and electronic fields, mechanical properties as well as excellent heat resistance are required.

However, a general polycarbonate resin is selectively infiltrated into a specific solvent, has no resistance, and has good creep resistance against a static load. However, when the temperature and various environmental conditions are mated, the polycarbonate resin is relatively easily broken and the resistance against dynamic load is complicated .

Accordingly, researches for increasing the heat resistance of polycarbonate resins have been continuously conducted, and as a result, high heat-resistant polycarbonate resins have been developed (for example, U.S. Patent No. 5,070,177, U.S. Patent No. 4,918,149). Generally, such a high heat resistant polycarbonate has modified the bisphenol A to introduce a stereosubstituted substituent at the ortho position to increase the hydrolysis property and increase the heat distortion temperature.

However, such a conventional high heat-resistant polycarbonate resin has a problem that impact resistance is remarkably lower than that of a general polycarbonate resin.

SUMMARY OF THE INVENTION The present invention has been made to overcome the problems of the prior art as described above, and it is an object of the present invention to provide a thermoplastic polycarbonate copolymer resin which is remarkably improved in heat resistance compared to conventional high heat resistant polycarbonate resin and has excellent balance of physical properties such as transparency and fluidity, And to provide a molded article containing the same.

(A) a polyarylene ether sulfone compound represented by the following formula (1); And (B) a polycarbonate block, wherein the polycarbonate block copolymer comprises:

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

X each independently represents a halogen atom or a hydroxy group,

m and n are each independently an integer of 0 to 4,

y is an integer from 2 to 150;

According to one embodiment of the present invention, the polyarylene ether sulfone compound of formula (1) is obtained by reacting a dihydroxy diaryl sulfone compound represented by the following formula (2-1) and a dihalogenenedialyl sulfone compound represented by the following formula Lt; RTI ID = 0.0 > of: < / RTI >

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

Hal represents a halogen atom,

m and n are each independently an integer of 0 to 4;

According to another aspect of the present invention, there is provided a process for producing a polyarylene ether compound, which comprises: (1) condensing a dihydroxydiarylsulfone compound represented by Formula (2-1) and a dihalogenenedialylsulfone compound represented by Formula (2-2) Polymerizing the sulfone oligomer; And (2) a step of copolymerizing the polyarylene ether sulfonyl oligomer obtained in the step (1) and the polycarbonate in the presence of a polymerization catalyst.

 According to another aspect of the present invention, there is provided a molded article comprising the polycarbonate block copolymer.

The polycarbonate block copolymer according to the present invention is excellent in heat resistance and also has excellent balance of physical properties such as impact resistance, transparency and fluidity, and is suitable for use in office equipment, housings for electric and electronic products, Can be usefully used.

Hereinafter, the present invention will be described in more detail.

(A) a polyarylene ether sulfone compound

The polycarbonate block copolymer of the present invention contains a polyarylene ether sulfone compound represented by the general formula (1) as a repeating unit.

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, Branched alkyl of 1 to 10 carbon atoms, branched alkyl of 1 to 6 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, cycloalkylalkyl of 4 to 10 carbon atoms, or aryl of 6 to 10 carbon atoms,

Each X independently represents a halogen atom (i.e., F, Cl, Br or I, more particularly Cl) or a hydroxy group,

m and n are each independently an integer of 0 to 4,

y is an integer of 2 to 150, more specifically an integer of 5 to 120.

According to one embodiment of the present invention, the polyarylene ether sulfone compound of formula (1) is obtained by reacting a dihydroxy diaryl sulfone compound represented by the following formula (2-1) and a dihalogenenedialyl sulfone compound represented by the following formula Lt; RTI ID = 0.0 > of: < / RTI >

[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)

R ₁ , R ₂ , m and n are each as defined in the above formula (1)

Hal represents a halogen atom (i.e., F, Cl, Br or I, more particularly Cl).

According to one embodiment, the condensation reaction of the dihydroxy diaryl sulfone compound and the dihalogenenedio aryl sulfone (e.g., dichlorodiphenyl sulfone) compound is carried out in the presence of an alkali metal salt catalyst in a reaction solvent at a temperature of, for example, Temperature and atmospheric pressure for 5 to 10 hours. Examples of the solvent for the condensation reaction include N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), dimethylacetamide (DMAc), dimethylformamide (DMF), sulfolane , Diphenylsulfone (DPS), dimethylsulfone (DMS), chlorobenzene, tetrahydrofuran (THF), or a mixed solvent thereof may be used. After completion of the condensation reaction, the reaction product is diluted (the same solvent as the reaction solvent can be used as the diluting solvent), and the alkali metal halide produced in the reaction (the alkali metal from the alkali metal salt catalyst and the di A salt of a halogen derived from a halogenated sulfone compound such as KCl) is removed by a decanter, a centrifuge or the like using, for example, a Celite filter or a specific gravity difference. Thereafter, the diluted and filtered reaction product is precipitated in a solvent (for example, an alcohol such as methanol or water), and then washed with water or the like to obtain a polyarylene ether sulfone compound.

The reaction molar ratio of the dihydroxydiarylsulfone compound to the dihalogenenedialyl sulfone compound may be from 1: 0.9 to 1: 1.1, and more specifically from 1: 0.95 to 1: 1.05. A polyarylene ether sulfone compound can be obtained in a high yield in a reaction molar ratio within the above range.

The polyarylene ether sulfone compound may have a number average molecular weight of 500 to 30,000 g / mol as measured by gel permeation chromatography (GPC), but is not limited thereto.

(B) Polycarbonate block

The polycarbonate block contained as a repeating unit in the polycarbonate block copolymer of the present invention is introduced into the copolymer of the present invention by reacting a polycarbonate oligomer with the polyarylene ether sulfone compound of the above formula (1).

There is no particular limitation on the method for producing the polycarbonate oligomer. For example, it may be produced by a phosgene method in which a divalent phenol compound and phosgene are mixed together, but the present invention is not limited thereto.

The divalent phenol compound used for preparing the polycarbonate oligomer may be, for example, a compound represented by the following formula (3).

(3)

In Formula 3, L is a straight, branched or cyclic alkylene group having no functional group or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, phenyl, isobutylphenyl, Or a cyclic alkylene group. Preferably, L may be a straight, branched or cyclic alkylene group having 1 to 10 carbon atoms. R ₃ and R ₄ may independently represent a halogen atom, a straight, branched or cyclic alkyl group. m and n independently represent an integer of 0 to 4;

The compound of formula (3) is, for example, selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) Pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy- Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, p Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4-bis (4-hydroxyphenyl) propane, 1,4-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2- (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis Bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenz Benzophenone, 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other dihydric phenols can be found in U.S. Patents US 2,999,835, US 3,028,365, US 3,153,008, US 3,334,154, and US 4,131,575, and the dihydric phenols may be used singly or in combination with one another Can be used in combination.

According to one embodiment of the present invention, the divalent phenol compound (for example, bisphenol A) is added to an aqueous alkaline solution, and the resultant mixture is mixed with an organic solvent (for example, dichloromethane) To prepare an oligomeric polycarbonate wherein the molar ratio of the phosgene to the divalent phenol compound can be maintained in the range of about 1: 1 to 1.5: 1, preferably about 1: 1 to 1.2: 1, The molecular weight of the oligomeric polycarbonate produced may be from 1,000 to 2,000.

According to another embodiment of the present invention, the divalent phenol compound (for example, bisphenol A) is added to an alkaline aqueous solution, and the resultant mixture is mixed with an organic solvent (for example, dichloromethane) (Wherein the molar ratio of phosgene: divalent phenol compound may be maintained in the range of about 1: 1 to 1.5: 1, preferably about 1: 1 to 1.2: 1), wherein the molecular weight modifier and catalyst The polycarbonate oligomer can be formed.

The polycarbonate oligomerization reaction can be generally carried out at a temperature in the range of about 15 to 60 占 폚. For adjusting the pH of the reaction mixture, alkali metal hydroxides may be introduced into the reaction mixture. The alkali metal hydroxide may be, for example, sodium hydroxide.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the polycarbonate may be used. The monofunctional material may be selected from, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Phenol-based derivatives such as isononylphenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) may be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. The polymerization catalyst may be, for example, triethylamine (TEA), and the phase transfer catalyst may be a compound represented by the following general formula (4).

[Chemical Formula 4]

(R ₅ ) ₄ Q ⁺ Z ^-

In Formula 4, R ₅ may independently represent an alkyl group having 1 to 10 carbon atoms, Q may represent nitrogen or phosphorus, and Z may represent a halogen atom or -OR ₆ . Here, R ₆ may represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The phase transfer catalysts include, for _{example, [CH 3 (CH 2)} 3] 4 NZ, [CH 3 (CH 2) 3] 4 PZ, [CH 3 (CH 2) 5] 4 NZ, [CH 3 (CH 2 ) ₆ ] ₄ NZ, [CH ₃ (CH ₂ ) ₄ ] ₄ NZ, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NZ and CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NZ. Wherein Z may be Cl, Br or -OR < ₆ >. Here, R ₆ may be a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.1 to 10% by weight of the reaction mixture. When the content of the phase-transfer catalyst is less than 0.1% by weight, the reactivity may be deteriorated. When the amount of the phase-transfer catalyst is more than 10% by weight, precipitation may occur in the precipitate, and the transparency of the resultant copolymer may be deteriorated.

After the polycarbonate oligomer is formed as described above, the organic phase dispersed in methylene chloride is washed with alkali and separated. Subsequently, the organic phase is washed with a 0.1N hydrochloric acid solution and then washed repeatedly with distilled water 2-3 times.

When the cleaning is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level and granulation is performed using a predetermined amount of secondary distilled water at 40 to 80 ° C. If the temperature of the second distilled water is less than 40 캜, the assembling time may be excessively long due to a slower granulation speed, and it may be difficult to obtain a polycarbonate having a certain particle size if the temperature exceeds 80 캜. When the assembly is completed, it is preferable to firstly dry at 100 to 110 ° C for 5 to 10 hours and secondly to 110 to 120 ° C for 5 to 10 hours.

The viscosity average molecular weight of the prepared branched polycarbonate oligomer may preferably be 1,000 to 30,000, more preferably 1,000 to 15,000. If the viscosity average molecular weight is less than 1,000, the mechanical properties may be significantly deteriorated. If the average molecular weight is more than 30,000, the copolymerization reactivity may be deteriorated.

(C) a block copolymer

The block copolymer of the present invention comprises (A) the polyarylene ether sulfone compound of formula (1) and the polycarbonate block (B) described above as repeating units. The polycarbonate block (B) includes both linear polycarbonate blocks, branched polycarbonate blocks and combinations thereof. According to embodiments of the present invention, a linear polycarbonate block is predominant, but a branched polycarbonate block is also possible, and both may be used in combination.

The amount of the polyarylene ether sulfone compound (A) contained in the block copolymer of the present invention is preferably from 0.5 to 50 mol (mol) based on 100 mol (mol)% of the total molar amount of the monomer compound constituting the copolymer %. If the relative amount of the compound of formula (I) is less than the lower limit, the heat resistance may be lowered. On the other hand, if the relative amount is less than the above range, the properties such as transparency, fluidity and impact strength may deteriorate and the manufacturing cost may increase.

Alternatively, the amount of the polyarylene ether sulfone compound (A) contained in the block copolymer of the present invention is preferably from 0.5 to 50% by weight, based on 100% by weight of the total weight of the monomer compounds constituting the copolymer, More preferably from 5 to 50% by weight, and still more preferably from 9 to 45% by weight. If the relative amount of the compound of formula (I) is less than the lower limit, the heat resistance may be lowered. On the other hand, if the relative amount is less than the above range, the properties such as transparency, fluidity and impact strength may deteriorate and the manufacturing cost may increase.

The block copolymer of the present invention has a viscosity average molecular weight (Mv), as measured in a methylene chloride solution, of preferably 10,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 15,000 to 70,000. If the viscosity average molecular weight of the copolymer is less than 10,000, the mechanical properties may be significantly deteriorated. If the viscosity average molecular weight is more than 200,000, the melt viscosity may increase, which may cause problems in processing the resin.

The block copolymer of the present invention can be produced by preparing a polycarbonate oligomer as described above, and then copolymerizing the polycarbonate oligomer thus prepared with the compound of the formula (1).

Therefore, according to another aspect of the present invention, there is provided a process for producing a polyarylate compound, comprising the steps of: (1) condensing a dihydroxydiarylsulfone compound represented by Formula (2-1) and a dihalogenenedialylsulfone compound represented by Formula (2-2) Polymerizing the phenylene ether oligomer; And (2) a step of copolymerizing the polyarylene ether sulfonyl oligomer obtained in the step (1) and the polycarbonate in the presence of a polymerization catalyst.

As the polymerization catalyst, for example, basic catalysts such as alkali metal hydroxides, alkylammonium salts, alkylamines and the like can be used.

According to one embodiment of the present invention, the block copolymer of the present invention can be prepared by adding the compound of the formula (1) to the organic phase-water mixture containing the previously prepared polycarbonate oligomer and introducing the molecular weight adjuster and the catalyst stepwise have. The molecular weight regulator and the catalyst are as described above.

Also, according to one embodiment, the organic phase in which the produced copolymer is dispersed in methylene chloride is subjected to alkali washing and separation, followed by washing the organic phase with 0.1N hydrochloric acid solution and then repeating the reaction with distilled water for 2 to 3 times After the washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to be constant, and granulation is performed using a predetermined amount of pure water at 40 to 80 ° C. If the pure water temperature is less than 40 ° C, the assembling speed is decreased and the assembling time may become very long. If the pure water temperature exceeds 80 ° C, it may become difficult to obtain the shape of the copolymer at a constant size. When the assembly is completed, it is preferable to firstly dry at 100 to 110 ° C for 5 to 10 hours and secondly at 110 to 120 ° C for 5 to 10 hours.

The block copolymer according to the present invention is excellent in heat resistance, and is excellent in balance of physical properties such as transparency and fluidity, and thus is required to have heat resistance such as optical materials, automobile parts (internal and external parts), office equipment, . ≪ / RTI >

Therefore, according to another aspect of the present invention, there is provided a molded article comprising the polycarbonate block copolymer of the present invention.

 The method of molding the polycarbonate block copolymer of the present invention into a molded product is not particularly limited and a molded article can be produced by a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[Example]

Preparation Example 1: Preparation of polyarylene ether sulfone compound of formula (5)

A condenser was attached to a 500 mL three-necked flask, and 4,4'-dihydroxydiphenyl sulfone (DHDPS) (1.0 mole), 4,4'-dichlorodiphenyl sulfone 1.0 mole of 4,4'-dichlorodiphenyl sulfone, DCDPS), 1.1 mole of potassium carbonate, 10.1 mole of N-methyl-2-pyrrolidone (NMP) 1.11 mole). The reaction mixture was rapidly heated to a reaction temperature (170 ° C), and it was confirmed that the chlorobenzene added to the co-solvent was azeotropically distilled out of the reaction by-product H ₂ O as the reaction time elapsed. After a reaction time of 6 hours at a temperature of 192 ° C, the final reaction mixture turned dark brown and the viscosity of the reaction mixture was visually confirmed. The final reaction mixture was cooled to room temperature and then diluted with previously prepared solvent NMP. The diluted reaction mixture was filtered through celite and then precipitated in methanol. The precipitated product was washed with distilled water and filtered to obtain a polyarylene ether sulfone compound of formula (5).

[Chemical Formula 5]

Preparation Example 2: Preparation of polyarylene ether sulfone compound of formula (6)

A condenser was attached to a 500 mL three-necked flask, and 4,4'-dihydroxydiphenyl sulfone (DHDPS) (1.0 mole), 4,4'-dichlorodiphenyl sulfone 1.0 mole of 4,4'-dichlorodiphenyl sulfone, DCDPS), 1.1 mole of potassium carbonate, 10.1 mole of N-methyl-2-pyrrolidone (NMP) 1.11 mole). The reaction mixture was rapidly heated to a reaction temperature (170 ° C), and it was confirmed that the chlorobenzene added to the co-solvent was azeotropically distilled out of the reaction by-product H ₂ O as the reaction time elapsed. After a reaction time of 10 hours at a temperature of 192 캜, the final reaction mixture turned dark brown, and the viscosity of the reaction mixture was visually confirmed. The final reaction mixture was cooled at room temperature and then diluted with a solvent NMP previously prepared. The diluted reaction mixture was filtered through celite and then precipitated in methanol. The precipitated product was washed with distilled water and filtered, and then dried to obtain polyarylene ether sulfone compound (6).

[Chemical Formula 6]

Production Example 3: Preparation of polyarylene ether sulfone compound of formula (7)

A condenser was attached to a 500 mL three-necked flask, and under a nitrogen atmosphere, 4,4'-dihydroxydiphenyl sulfone (DHDPS) (1.05 mole), 4,4'-dichlorodiphenyl sulfone 1.0 mole of 4,4'-dichlorodiphenyl sulfone, DCDPS), 1.1 mole of potassium carbonate, 10.1 mole of N-methyl-2-pyrrolidone (NMP) 1.11 mole). The reaction mixture was rapidly heated to a reaction temperature (170 ° C), and it was confirmed that the chlorobenzene added to the co-solvent was azeotropically distilled out of the reaction by-product H ₂ O as the reaction time elapsed. After a reaction time of 6 hours at a temperature of 192 ° C, the final reaction mixture turned dark brown and the viscosity of the reaction mixture was visually confirmed. The final reaction mixture was cooled at room temperature and then diluted with a solvent NMP previously prepared. The diluted reaction mixture was filtered through celite and then precipitated in methanol. The precipitated product was washed with distilled water and filtered to obtain a polyarylene ether sulfone compound of formula (7).

(7)

Production Example 4: Preparation of polyarylene ether sulfone compound of formula (8)

A condenser was attached to a 500 mL three-necked flask, and under a nitrogen atmosphere, 4,4'-dihydroxydiphenyl sulfone (DHDPS) (1.05 mole), 4,4'-dichlorodiphenyl sulfone 1.0 mole of 4,4'-dichlorodiphenyl sulfone, DCDPS), 1.1 mole of potassium carbonate, 10.1 mole of N-methyl-2-pyrrolidone (NMP) 1.11 mole). The reaction mixture was rapidly heated to a reaction temperature (170 ° C), and it was confirmed that the chlorobenzene added to the co-solvent was azeotropically distilled out of the reaction by-product H ₂ O as the reaction time elapsed. After a reaction time of 8 hours at a temperature of 192 캜, the final reaction mixture turned dark brown, and the viscosity of the reaction mixture was visually confirmed. The final reaction mixture was cooled at room temperature and then diluted with a solvent NMP previously prepared. The diluted reaction mixture was filtered through celite and then precipitated in methanol. The precipitated product was washed with distilled water and filtered to obtain a polyarylene ether sulfone compound of formula (8).

[Chemical Formula 8]

Production Example 5: Preparation of polycarbonate oligomer

(0.263 mol) of bisphenol A was dissolved in 330 ml (18.46 g, 0.462 mol) of 5.6 wt% sodium hydroxide aqueous solution in a 1 L three-necked flask, 26.0 g (0.263 mol) of phosgene was collected in methylene chloride, Lt; RTI ID = 0.0 > Slowly < / RTI > The external temperature was maintained at 0 ° C. The reaction product having passed through the tubular reactor was subjected to interfacial reaction in a nitrogen atmosphere for about 10 minutes to prepare an oligomeric polycarbonate having a viscosity average molecular weight of about 1,000. 215 mL of the organic phase and 322 mL of the aqueous phase were collected in a mixture containing the oligomeric polycarbonate prepared above, and 1.383 g (9.21 mmol, p-tert-butylphenol (PTBP), 3.5 mol% based on bisphenol A) of tetrabutylammonium chloride 0.131 mL of an aqueous solution of 15 wt% triethylamine (TEA) was mixed with 0.731 g (2.63 mmol, 1 mol% based on bisphenol A) of tetrabutyl ammonium chloride (TBACl) and reacted for 30 minutes to obtain a polycarbonate oligomer solution .

Production Example 6: Preparation of polycarbonate oligomer

(0.263 mol) of bisphenol A was dissolved in 330 ml (18.46 g, 0.462 mol) of 5.6 wt% sodium hydroxide aqueous solution in a 1 L three-necked flask, 26.0 g (0.263 mol) of phosgene was collected in methylene chloride, Lt; RTI ID = 0.0 > Slowly < / RTI > The external temperature was maintained at 0 ° C. The reaction product having passed through the tubular reactor was subjected to interfacial reaction in a nitrogen atmosphere for about 10 minutes to prepare an oligomeric polycarbonate having a viscosity average molecular weight of about 1,000. 215 mL of the organic phase and 322 mL of the aqueous phase were collected in a mixture containing the oligomeric polycarbonate prepared above and 0.198 g (1.32 mmol, p-tert-butylphenol (PTBP), 0.5 mol% based on bisphenol A) and tetrabutylammonium chloride (1.63 mmol, 1 mol% based on bisphenol A) and 0.1 mL of 15 wt% triethylamine (TEA) were mixed and reacted for 30 minutes to obtain a polycarbonate oligomer solution .

Example 1: Preparation of block copolymer

15 g of the compound of Formula 5 (1 mol% based on bisphenol A; 9 wt% based on the total amount of the monomer constituting the copolymer) was added to the polycarbonate oligomer solution prepared in Production Example 5, and after the layer separation After collecting only the organic phase, the same amount of methylene chloride (283 g) as the organic phase, 110 mL of a 1.1 N sodium hydroxide aqueous solution (20 vol% based on the total mixture) and 15 μL of 15 wt% triethylamine were mixed and reacted for 1 hour 167 μL of 15% by weight triethylamine and 128 g of methylene chloride were added and reacted for 1 hour. After separating the layers, pure water was added to the organic phase whose viscosity was increased, followed by washing with alkali, followed by separation. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. After the washing was completed and the concentration of the organic phase was kept constant, the organic phase was assembled using a predetermined amount of secondary distilled water at 76 ° C. After the assembly was completed, the block copolymer was firstly dried at 110 DEG C for 8 hours and then at 120 DEG C for 10 hours. The physical properties of the prepared copolymer were measured, and the results are shown in Table 1 below.

Example 2: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1, except that 75 g of the compound of the formula (5) (5 mol% based on the bisphenol A, 45 wt% based on the total amount of the monomer compounds constituting the copolymer) Respectively. The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 3: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1 except that 100 g of the compound of the formula (6) (1 mol% based on the bisphenol A) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 4: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1 except that 74 g of the compound of the formula (7) (5 mol% based on the bisphenol A) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 5: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1 except that 41 g of the compound of the formula (8) (1 mol% based on the bisphenol A) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 6: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1, except that the polycarbonate oligomer solution prepared in Preparation Example 5 was used instead of the polycarbonate oligomer solution prepared in Preparation Example 5. The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 7: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1 except that 75 g of the compound of the formula (6) (45% by weight based on the total amount of the monomer compounds constituting the copolymer) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 8: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1, except that 75 g of the compound of the formula (7) (45% by weight based on the total amount of the monomer compounds constituting the copolymer) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Example 9: Preparation of block copolymer

A block copolymer was prepared in the same manner as in Example 1, except that 75 g of the compound of the formula (8) (45% by weight based on the total amount of the monomer compounds constituting the copolymer) was used instead of 15 g of the compound of the formula (5). The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Comparative Example 1

A linear polycarbonate having a viscosity average molecular weight of 21,200 was prepared by an interfacial polymerization method. The physical properties of the produced linear polycarbonate were measured, and the results are shown in Table 1 below.

Comparative Example 2

A linear polycarbonate having a viscosity average molecular weight of 71,200 was prepared by an interfacial polymerization method. The physical properties of the produced linear polycarbonate were measured, and the results are shown in Table 1 below.

Comparative Example 3

A block copolymer was prepared in the same manner as in Example 1, except that 0.75 g (0.45% by weight based on the total amount of the monomer compounds constituting the copolymer) of the compound of the formula (5) was used. The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

Comparative Example 4

A block copolymer was prepared in the same manner as in Example 1, except that 90 g of the compound of the formula (5) was used in an amount of 54% by weight based on the total amount of the monomer compounds constituting the copolymer. The properties of the prepared copolymer were measured and the results are shown in Table 1 below.

The physical properties shown in Table 1 below were measured after drying the resin prepared in the above Examples and Comparative Examples at 120 DEG C for 24 hours. The copolymer identification method and physical property measurement method are as follows.

(1) Viscosity average molecular weight: The viscosity of the methylene chloride solution was measured at 20 占 폚 using a Ubbelohde viscometer, and the intrinsic viscosity [?] Was calculated from the following formula.

^{[η] = 1.23X10 - 5 Mv} 0 .83

(2) Impact strength: The impact strength was measured at room temperature using an impact tester (RESIL IMPACTOR, manufactured by CEAST).

(3) Total light transmittance: A specimen having a thickness of 3 mm was evaluated according to ASTM D1003.

(4) Glass transition temperature: The glass transition temperature was measured using a differential scanning calorimeter (Perkin-Elmer DSC-7 & Robotic).

As can be seen from Table 1, the polycarbonate block copolymers prepared in Examples 1 to 9 according to the present invention exhibited remarkably excellent heat resistance as compared with the linear polycarbonates of Comparative Examples 1 and 2, Similar levels were maintained.

In addition, in the case of Comparative Example 3 (containing 0.45 wt% of polyarylene ether sulfone compound based on the total amount of the monomer compounds constituting the copolymer), the heat resistance remarkably deteriorated.

In the case of Comparative Example 4 (containing 54% by weight of the polyarylene ether sulfone compound based on the total amount of the monomer compounds constituting the copolymer), the polyarylene ether sulfone compound contained more than 50% by weight and heat resistance was improved , The impact strength is remarkably decreased.

That is, in order to maintain the impact strength and transparency at an appropriate level while improving the heat resistance of the polycarbonate block copolymer, the content of the polyarylene ether sulfone compound is preferably maintained at 0.5 to 50 wt%.

Claims (13)

(A) a polyarylene ether sulfone compound represented by the following formula (1); And (B) a polycarbonate block comprising:
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
X each independently represents a halogen atom or a hydroxy group,
m and n are each independently an integer of 0 to 4,
y is an integer from 2 to 150; The polyarylene ether sulfone compound of claim 1, wherein the polyarylene ether sulfone compound of formula (1) is a condensation reaction product of a dihydroxy diaryl sulfone compound represented by the following formula (2-1) and a dihalogenenedialyl sulfone compound represented by the following formula Wherein the polycarbonate block copolymer comprises:
[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)
R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
Hal represents a halogen atom,
m and n are each independently an integer of 0 to 4; The polycarbonate block copolymer according to claim 2, wherein the reaction molar ratio of the dihydroxydiarylsulfone compound: dihalogenediaryl sulfone compound is 1: 0.9 to 1: 1.1. The polycarbonate block copolymer according to claim 1, wherein the polyarylene ether sulfone compound has a number average molecular weight of 500 to 30,000 g / mol. The polycarbonate block copolymer according to claim 1, wherein the polycarbonate block is derived from a polycarbonate oligomer produced by a phosgene process in which a divalent phenol compound and phosgene are mixed together. The polycarbonate block copolymer according to claim 5, wherein the divalent phenol compound is bisphenol A. The polycarbonate block copolymer according to claim 5, wherein the polycarbonate oligomer has a viscosity average molecular weight of 1,000 to 30,000. 2. The polyarylene ether sulfone compound according to claim 1, wherein the amount of the polyarylene ether sulfone compound (A) represented by the formula (1) contained in the copolymer is 0.5 to 100 mol% based on the total molar amount of the monomer compound constituting the copolymer. By mole to 50% by mole. The polyarylene ether sulfone compound according to claim 1, wherein the amount of the polyarylene ether sulfone compound (A) represented by the formula (1) contained in the copolymer is 0.5 to 50 wt% based on the total weight of the monomer compound constituting the copolymer %. ≪ / RTI > The polycarbonate block copolymer according to claim 1, wherein the block copolymer has a viscosity average molecular weight (Mv) of 10,000 to 200,000. (1) polymerizing a polyarylene ether sulfonyl oligomer by condensation reaction of a dihydroxy diaryl sulfone compound represented by the following formula (2-1) and a dihalogenenedialyl sulfone compound represented by the following formula (2-2); And
(2) copolymerizing the polyarylene ether sulfonyl oligomer obtained in the step (1) and polycarbonate in the presence of a polymerization catalyst.
Method of preparing polycarbonate block copolymer:
[Formula 2-1]

[Formula 2-2]

In the above Formulas (2-1) and (2-2)
R ₁ and R ₂ each independently represent an alkyl having 1 to 10 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, a cycloalkylalkyl having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
Hal represents a halogen atom,
m and n are each independently an integer of 0 to 4; A molded article comprising the polycarbonate block copolymer of any one of claims 1 to 10. The molded article according to claim 12, which is an optical material or an automobile part.