KR101448058B1 - Polycarbonate resin composition having improved low-temperature impact resistance and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a process for producing the same. More specifically, the present invention relates to a polycarbonate resin composition and a process for producing the polycarbonate resin composition, And a method for producing the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having improved low temperature impact resistance and a method of manufacturing the same. 2. Description of the Related Art Polycarbonate resin compositions having improved impact resistance at low temperatures,

The present invention relates to a polycarbonate resin composition and a process for producing the same. More specifically, the present invention relates to a polycarbonate resin composition and a process for producing the polycarbonate resin composition, And a method for producing the same.

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and is excellent in dimensional stability, heat resistance and optical transparency, and is widely used in industrial applications. However, polycarbonate has excellent impact resistance at room temperature, but has a weak point that the impact resistance sharply drops at low temperatures.

Studies on various copolymers continue to improve these vulnerabilities, and it has become known that polysiloxane-polycarbonate copolymers have relatively good impact resistance at low temperatures. However, currently used polysiloxane-polycarbonate copolymers do not exhibit satisfactory low-temperature impact resistance in an industrially satisfactory level, and cause deterioration of other properties such as fluidity and heat resistance.

Accordingly, development of a polycarbonate resin composition capable of remarkably improving low-temperature impact resistance while maintaining excellent physical properties inherent to polycarbonate such as fluidity and heat resistance is required.

United States Patent Application Publication No. 2003/0105226

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in an effort to solve the problems of the prior art as described above, and an object of the present invention is to provide a polycarbonate resin composition having improved impact resistance at low temperature while maintaining excellent flowability and heat resistance.

The present invention provides a polycarbonate resin composition comprising a polysiloxane-polycarbonate copolymer and a polycarbonate, wherein the content of the siloxane in the polysiloxane-polycarbonate copolymer is 10 to 35% by weight.

In another aspect of the present invention, there is also provided a process for preparing a polysiloxane-polycarbonate intermediate, comprising: reacting a hydroxy-terminated siloxane with an oligomeric polycarbonate under an interface reaction condition to form a polysiloxane-polycarbonate intermediate; Polymerizing the intermediate with a first polymerization catalyst to produce a polysiloxane-polycarbonate copolymer having a siloxane content of 10 to 35% by weight; And a step of mixing the polysiloxane-polycarbonate copolymer and the polycarbonate to prepare a polycarbonate resin composition.

The polycarbonate resin composition according to the present invention can significantly improve the low-temperature impact resistance by mixing the polysiloxane-polycarbonate copolymer having a specific range of siloxane content with the polycarbonate, and at the same time, has excellent impact resistance at room temperature, fluidity and heat resistance And can be suitably used for various purposes such as a helmet, an automobile part, and a cellular phone housing.

Hereinafter, the present invention will be described in more detail. The objects, features and advantages of the present invention will be easily understood by the following embodiments. The present invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments disclosed herein are provided so that the disclosure may be thorough and complete, and that those skilled in the art will be able to convey the spirit of the invention to those skilled in the art. Therefore, the present invention is not limited by the following exemplary explanations and embodiments.

As used herein, the term "reaction product" means a material in which two or more reactants are formed by reaction.

In addition, although the terms "first", "second" and the like are used herein to describe a polymerization catalyst, the polymerization catalyst is not limited by these terms. These terms are merely used to distinguish polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be the same kind of catalyst or different kinds of catalysts.

The letter "R" used to represent hydrogen, a halogen atom and / or a hydrocarbon group in the formulas described in the present specification has a subscript indicated by a numeral, but the letter "R" But is not limited thereto. The "R" represents, independently of each other, hydrogen, a halogen atom and / or a hydrocarbon group. For example, the "R" s may represent the same hydrocarbon group or may represent other hydrocarbon groups, irrespective of whether two or more "R" have the same or different numbers of subscripts.

[Polycarbonate resin composition]

The polycarbonate resin composition according to the present invention comprises a polysiloxane-polycarbonate copolymer and a polycarbonate, and the content of the siloxane in the polysiloxane-polycarbonate copolymer is 10 to 35% by weight.

Polysiloxane-polycarbonate copolymer (Si-PC)

The polysiloxane-polycarbonate copolymer contained in the polycarbonate resin composition of the present invention may contain a hydroxy-terminated siloxane of the following general formula (1a) or (1) and a polycarbonate block of the following general formula (4) as repeating units.

[Formula 1a]

In formula (1a)

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group. For example, the halogen atom may be Cl or Br, and the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms such as methoxy, Ethoxy or propoxy, and the aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms. For example, R ₂ is an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, An aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

m independently represents an integer of 0 to 4;

n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100.

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다.In one embodiment, the hydroxy-terminated siloxane of formula (Ia) is a siloxane monomer of Dow Cominga

) May be used, but the present invention is not limited thereto.

[Chemical Formula 1]

R ₁ , R ₂ , R _3, m and n are as defined in the above formula (1a), and A represents a structure represented by the following formula (2) or (3)

(2)

In Formula 2,

Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (e.g., a cycloalkylene group having 3 to 6 carbon atoms), or a halogen atom, an alkyl group, an alkoxy Or an unsubstituted mono- or polycyclic arylene group having 6 to 30 carbon atoms, which is substituted with an aryl group or a carboxyl group. For example, Y is an aliphatic group substituted with a halogen atom or an unsubstituted aliphatic group, an aliphatic group containing an oxygen, nitrogen or sulfur atom in the main chain, or an aryl group derived from bisphenol A, resorcinol, hydroquinone or diphenyl phenol And may be represented, for example, by the following formulas (2a) to (2h).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(3)

In Formula 3,

R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aromatic / aliphatic mixed hydrocarbon group or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, R ₄ may have a structure including halogen, oxygen, nitrogen, or sulfur in addition to carbon atoms. For example, R < ₄ > may be phenyl, chlorophenyl or tolyl (preferably phenyl).

In one embodiment, the hydroxy-terminated siloxane of Formula 1 may be the reaction product of a hydroxy-terminated siloxane of Formula 1a with an acyl compound.

Here, the acyl compound may have a mixed structure including, for example, aromatic, aliphatic, or both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms. When the acyl compound is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further contain a halogen, an oxygen, a nitrogen or a sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 1 may be the reaction product of the hydroxy-terminated siloxane of Formula 1a with a diisocyanate compound.

Here, the diisocyanate compound may be, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate or 4,4'-methylenediphenyl diisocyanate. (4,4'-methylenediphenyl diisocyanate).

In another embodiment, the hydroxy-terminated siloxane of Formula 1 may be the reaction product of the hydroxy-terminated siloxane of Formula 1a with a phosphorus-containing compound (aromatic or aliphatic phosphate compound).

Here, the phosphorus-containing compound may be represented by the following formula (1b).

[Chemical Formula 1b]

In Formula 1b, R ₄ is as defined in Formula 3, and Z independently represents a phosphorus atom, a halogen atom, a hydroxyl group, a carboxyl group, an alkyl group (having 1 to 20 carbon atoms), an alkoxy group, or an aryl group.

Preferably, the polysiloxane-polycarbonate copolymer comprises a hydroxyl-terminated siloxane of formula (1a) or formula (1) and a polycarbonate block of formula (4) as recurring units.

[Chemical Formula 4]

In Formula 4,

R ₅ is (C 1 to 20) alkyl group (e.g., an alkyl group having a carbon number of 1 to 13), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (e.g., an alkenyl group having 2 to 13), An alkoxy group (e.g., an alkoxy group having 1 to 13 carbon atoms), a halogen atom, or an aromatic hydrocarbon group substituted or unsubstituted with nitro and having 6 to 30 carbon atoms.

Here, the aromatic hydrocarbon group may be derived from a compound having the structure of the following formula (4a).

[Chemical Formula 4a]

In the above formula (4a)

X is an alkylene group, a linear, 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, naphthyl, Lt; / RTI > Preferably, X is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.

R ₆ independently represents a hydrogen atom, a halogen atom, or an alkyl group, for example, a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms) having 1 to 20 carbon atoms.

n and m independently represent an integer of 0 to 4;

The compound of formula (4a) is, for example, selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ) - (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 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, Bis (4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) propane, 2,2- , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [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- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4- (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis -Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, ', 5,5'-tetramethyl-4,4'-dihydroxybenzophe , 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 functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

In the case of the carbonate precursor, as other monomers of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate or dimethyl carbonate can be used.

The content of the siloxane in the polysiloxane-polycarbonate copolymer contained in the polycarbonate resin composition of the present invention is 10 to 35% by weight, preferably 15 to 30% by weight, more preferably 20 to 30% by weight. If the content of the siloxane is less than 10% by weight based on the total weight of the copolymer, the effect of improving the low-temperature impact resistance required by the present invention may be insignificant. If the content exceeds 35% by weight, the relative content of the polycarbonate Physical properties such as fluidity, heat resistance, impact resistance at room temperature, and transparency may be deteriorated.

The polysiloxane-polycarbonate copolymer preferably has a viscosity average molecular weight (Mv) of 10,000 to 70,000, more preferably 15,000 to 30,000. 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 exceeds 70,000, the melt viscosity may increase, which may cause problems in processing the resin.

Polycarbonate (PC)

The polycarbonate included in the polycarbonate resin composition of the present invention together with the polysiloxane-polycarbonate copolymer is not particularly limited, and polycarbonate resins commonly used in the art can be used.

The polycarbonate preferably has a viscosity average molecular weight of 10,000 to 50,000, more preferably 15,000 to 35,000. If the viscosity average molecular weight of the polycarbonate is less than 10,000, the mechanical properties may be significantly deteriorated. If the viscosity average molecular weight is more than 50,000, the flowability may be lowered, which may cause problems in processing the resin.

The preferred weight ratio of the polysiloxane-polycarbonate copolymer to the polycarbonate contained in the polycarbonate resin composition of the present invention is 10:90 to 50:50, and more preferably 15:85 to 40:60. If the relative weight ratio of the copolymer to the polycarbonate is less than 10: 90, the effect of improving the low-temperature impact resistance required by the present invention may be insignificant. If the relative weight ratio exceeds 50:50, the fluidity, heat resistance, And the like may be deteriorated.

The preferred content of the siloxane in the polycarbonate resin composition of the present invention in which the polysiloxane-polycarbonate copolymer and the polycarbonate are mixed is 3 to 12% by weight, more preferably 4 to 10% by weight. When the content of the siloxane in the whole composition is in the range of 3 to 12% by weight, the low-temperature impact resistance can be greatly improved (about two times or more) while ensuring excellent flowability and impact resistance at room temperature.

[Method of producing polycarbonate resin composition]

The polycarbonate resin composition according to the present invention comprises the steps of reacting a hydroxy-terminated siloxane and an oligomeric polycarbonate under an interfacial reaction condition comprising an aqueous alkali solution and an organic phase to form a polysiloxane-polycarbonate intermediate; Polymerizing the intermediate with a first polymerization catalyst to produce a polysiloxane-polycarbonate copolymer having a siloxane content of 10 to 35% by weight; And mixing the prepared polysiloxane-polycarbonate copolymer with a polycarbonate.

In a preferred embodiment, the step of forming the intermediate comprises mixing the hydroxy-terminated siloxane and the oligomeric polycarbonate in a weight ratio of 10:90 to 35:65 (more preferably 15:85 to 30:70) . When the mixing ratio of the hydroxyl-terminated siloxane is less than 10, the effect of improving the low-temperature impact resistance required by the present invention may be insignificant. If the mixing ratio exceeds 35, the relative content of the polycarbonate in the copolymer decreases, Physical properties such as impact resistance and transparency may be lowered.

The polycarbonate used in the preparation of the polysiloxane-polycarbonate copolymer may be an oligomeric polycarbonate having a viscosity average molecular weight of 800 to 20,000 (more preferably 1,000 to 15,000). If the viscosity average molecular weight of the polycarbonate is less than 800, the molecular weight distribution may widen and the physical properties may be deteriorated. If the viscosity average molecular weight exceeds 20,000, the reactivity may be lowered.

In one embodiment, the oligomeric polycarbonate may be prepared by adding the above-mentioned dihydric phenol compound to an alkaline aqueous solution to form a phenol salt state, and then adding a phenol salt in a salt form into dichloromethane injected with a phosgene gas . For oligomer preparation, it is desirable to maintain the molar ratio of phosgene to bisphenol in the range of about 1: 1 to 1.5: 1, more preferably about 1: 1 to 1.2: 1. If the molar ratio of phosgene to bisphenol is less than 1, the reactivity may be deteriorated. If the molar ratio of bisphenol to phosgene exceeds 1.5, the workability may be deteriorated due to an excessive molecular weight increase.

The oligomerization reaction may be generally carried out at a temperature in the range of about 15 to 60 DEG C, and an alkali metal hydroxide (e.g., sodium hydroxide) may be used to adjust the pH of the reaction mixture.

In one embodiment, the step of forming the intermediate comprises forming a mixture comprising a hydroxy terminated siloxane and an oligomeric polycarbonate, wherein the mixture comprises a phase transfer catalyst, a molecular weight modifier and a second polymerization catalyst Lt; / RTI > Also, the step of forming the intermediate may include forming a mixture comprising a hydroxy terminated siloxane and an oligomeric polycarbonate; And extracting the organic phase from the resulting mixture after the reaction of the hydroxy end siloxane with the oligomeric polycarbonate is completed, wherein the step of polymerizing the intermediate comprises the step of providing a first polymerization catalyst to the extracted organic phase May include.

Specifically, the polysiloxane-polycarbonate copolymer can be prepared by adding the hydroxy-terminated siloxane of the above formula (1a) or (1) to the organic phase-water mixture containing the polycarbonate and gradually introducing a molecular weight regulator and a catalyst.

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, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. As the polymerization catalyst, for example, triethylamine (TEA) can be used. As the phase transfer catalyst, for example, a compound of the following formula (5) can be used.

[Chemical Formula 5]

(R ₇ ) ₄ Q ⁺ X ^-

In the general formula (5), R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or -OR ₈ . Here, R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase-transfer catalyst, for example, _{[CH 3 (CH 2) 3} ] 4 NX, [CH 3 (CH 2) 3] 4 PX, [CH 3 (CH 2) 5] 4 NX, [CH 3 _{(CH 2) 6] 4 NX} , [CH 3 (CH 2) 4] 4 NX, CH 3 [CH 3 (CH 2) 3] 3 NX, CH 3 [CH 3 (CH 2) 2] can be a ₃ NX have. In the above formulas, X represents Cl, Br or -OR ₈ , wherein R ₈ represents 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 0.01 to 10% by weight, more preferably 0.1 to 10% by weight based on the total weight of the mixture of the hydroxy end siloxane and the oligomeric polycarbonate. If the content is less than 0.01% by weight, the reactivity may be deteriorated. If the content is more than 10% by weight, precipitates may precipitate or the transparency may be deteriorated.

In one embodiment, the polysiloxane-polycarbonate copolymer is prepared and then the organic phase dispersed in methylene chloride is alkaline cleaned and then separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. When 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 in the range of 30 to 100 ° C, preferably 60 to 80 ° C. If the pure water temperature is less than 30 ° C, the assembling speed is decreased and the assembling time may become very long. When the pure water temperature exceeds 100 ° C, it may become difficult to obtain the polycarbonate shape to a certain size. When the assembly is completed, drying is preferably performed at 100 to 120 ° C for 5 to 10 hours, more preferably at 100 to 110 ° C for 5 to 10 hours, and further at 110 to 120 ° C for 5 to 10 hours .

The method of mixing the polysiloxane-polycarbonate copolymer thus prepared with polycarbonate is not particularly limited. Preferably, the polysiloxane-polycarbonate copolymer and the polycarbonate are kneaded at a weight ratio of 10:90 to 50:50 to finally prepare the polycarbonate resin composition of the present invention.

Examples and Comparative Examples

Example 1

≪ Preparation of hydroxy-terminated siloxane &

Under nitrogen, 0.0666 mol of monomer BY16-799 from Dow Corning was dissolved in 100 mL of benzene and then 1,4-diazabicyclo [2,2,2] -octane (1,4-diazabicyclo [2,2,2 ] -oxane. 0.0333 mol of 4,4-methylene bis (phenyl isocyanate) (0.0333 mol) was dissolved in 200 mL of benzene under reflux in the above solution, followed by slow addition for 1 hour. The above solution was refluxed for 12 hours. After the solvent of the reaction solution was removed, it was dissolved in acetone and washed with hot distilled water. And dried in a vacuum oven for 24 hours. Thus, a hydroxy-terminated siloxane having a urethane bond represented by the following formula (6) was prepared. Hydrogen bonded to the first carbon of the aliphatic chain adjacent to the terminal phenyl group in the following formula (6) was confirmed at 2.75 ppm.

[Chemical Formula 6]

≪ Preparation of polysiloxane-polycarbonate copolymer >

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture were added 20 wt% of a hydroxyl-terminated siloxane having urethane bond of the above formula (6) dissolved in methylene chloride, 1.8 mL of tetrabutyl ammonium chloride (TBACI) 1.5 g of phenol (PTBP) and 275 15 of 15% by weight triethylamine (TEA) were mixed and reacted for 30 minutes. After the reaction, the oligomeric polycarbonate mixture was allowed to stand for separation. After the separation of layers, only the organic phase was sampled, and 170 g of aqueous sodium hydroxide solution, 370 g of methylene chloride and 300 15 of triethylamine of 15 wt% were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed with distilled water two to three times. After the washing was completed, the concentration of the organic phase was uniformly adjusted to 76 ° C using a predetermined amount of pure water. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. It was confirmed by H-NMR that the peak of the methylene group of the polysiloxane observed at 2.65 ppm, the peak of the methoxy group observed at 3.85 ppm, and the hydrogen peak of the benzene ring observed at 7.1 ppm to 7.5 ppm were observed.

≪ Preparation of polycarbonate resin composition >

The prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3022PJ, Mv: 21,000) were kneaded at a weight ratio of 40:60 to prepare a polycarbonate resin composition. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Example 2

≪ Preparation of hydroxy-terminated siloxane &

A condenser was attached to a 500 mL three-necked flask. 0.4 mol of monomer BY16-799 of Dow corning was dissolved in 300 mL of chloroform under nitrogen atmosphere, and 67 mL of triethylamine (TEA) catalyst was added. After 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform while the solution was being refluxed, it was added slowly for 1 hour and refluxed for 12 hours. After the solvent of the reaction solution was removed, the solution was dissolved in acetone and washed with hot distilled water. And then dried in a vacuum oven for 24 hours to prepare a hydroxy-terminated siloxane having an ester bond represented by the following formula (7). The hydrogen peak of the methylene group of the polysiloxane observed at 2.6 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.75 to 7.35 ppm .

(7)

≪ Preparation of polysiloxane-polycarbonate copolymer >

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 30 parts by weight of a hydroxyl-terminated siloxane having an ester bond of the above formula (7) dissolved in methylene chloride, 1.8 mL of tetrabutyl ammonium chloride (TBACl) Phenol (PTBP) and 275 트리 of triethylamine (TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. After the reaction, the oligomeric polycarbonate mixture was allowed to stand for separation. After the layer separation, only the organic phase was taken, and 170 g of aqueous sodium hydroxide solution, 360 g of methylene chloride and 300 μl of a 15% by weight aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed with distilled water two to three times. After the washing was completed, the concentration of the organic phase was uniformly adjusted to 76 ° C using a predetermined amount of pure water. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. H-NMR showed peaks of the methylene group of the polysiloxane observed at 2.6 ppm and 2.65 ppm and hydrogen peaks of the benzene ring of TCL observed at 8.35 ppm and hydrogen peaks of the benzene ring of the polysiloxane observed at 6.95 to 7.5 ppm Respectively.

≪ Preparation of polycarbonate resin composition >

The prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3022PJ, Mv: 21,000) were kneaded at a weight ratio of 20:80 to prepare a polycarbonate resin composition. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Example 3

Polysiloxane-polycarbonate copolymer was prepared using 20% by weight of the hydroxyl-terminated siloxane of the above formula (7), and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3027PJ, Mv: 24,600) were mixed at a weight ratio of 30:70 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Example 4

Polysiloxane-polycarbonate copolymer was prepared by using 20% by weight of the hydroxy-terminated siloxane represented by the following formula (8), and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3022PJ, Mv: 21,000) were mixed at a weight ratio of 30:70 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

[Chemical Formula 8]

BY16-753(다우 코닝사, Mn=3,000)

BY16-753 (Dow Corning, Mn = 3,000)

Example 5

Polysiloxane-polycarbonate copolymer was prepared by using 30 weight% of the hydroxy-terminated siloxane of Formula 8, and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3022PJ, Mv: 21,000) were mixed at a weight ratio of 15:85 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 1

Polysiloxane-polycarbonate copolymer was prepared using 8% by weight of the hydroxy-terminated siloxane of the above formula (7), and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3022PJ, Mv: 21,000) were mixed at a weight ratio of 60:40 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 2

Polysiloxane-polycarbonate copolymer was prepared by using 9 weight% of the hydroxy-terminated siloxane represented by the above formula (8), and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3027PJ, Mv: 24,600) were mixed at a weight ratio of 30:70 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 3

Polysiloxane-polycarbonate copolymer was prepared using 45% by weight of the hydroxyl-terminated siloxane of the above formula (8), and the prepared polysiloxane-polycarbonate copolymer and polycarbonate (Samyang 3027PJ, Mv: 24,600) were mixed at a weight ratio of 40:60 A polycarbonate resin composition was prepared in the same manner as in Example 1, except that the mixture was kneaded. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below. In the case of Comparative Example 3, injection molding was impossible and the low temperature impact strength could not be measured.

Comparative Example 4

Except that the polysiloxane-polycarbonate copolymer was prepared using 8 weight% of the hydroxy-terminated siloxane of the above formula (7), and the prepared polysiloxane-polycarbonate copolymer was used alone without being mixed with the polycarbonate. A polycarbonate resin composition was prepared in the same manner. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 5

Except that the polysiloxane-polycarbonate copolymer was prepared using 20 wt% of the hydroxy-terminated siloxane of the above formula (7), and the prepared polysiloxane-polycarbonate copolymer was used alone without being mixed with the polycarbonate. A polycarbonate resin composition was prepared in the same manner. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 6

A polycarbonate resin composition was prepared in the same manner as in Example 1, except that polycarbonate (Samyang, 3022PJ, Mv: 21,000) was used alone without polysiloxane-polycarbonate copolymer. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

Comparative Example 7

A polycarbonate resin composition was prepared in the same manner as in Example 1, except that polycarbonate (Samyang 3030PJ, Mv: 31,200) was used alone without polysiloxane-polycarbonate copolymer. The physical properties of the polycarbonate resin composition thus prepared were measured and reported in Table 1 below.

 [Table 1]

As shown in Table 1, it can be seen that the polycarbonate resin compositions prepared according to the Examples are superior in shock resistance and fluidity at room temperature and superior in low temperature impact strength as compared with the polycarbonate resin compositions prepared according to Comparative Examples .

The performance evaluation methods used in the above Examples and Comparative Examples are as follows.

(a) H-NMR (nuclear magnetic resonance spectroscope): Measured using Avance DRX 300 from Bruker.

(b) Viscosity average molecular weight (Mv): 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.

[?] = 1.23 x 10 ^-5 Mv ^0.83

(c) Impact strength: The impact strength was measured at room temperature and -50 캜 using an impact tester (RESIL IMPACTOR from CEAST).

(d) MI (Melt Index) : indicates the fluidity at constant temperature and load, in accordance with ASTM D1238 was measured at 300 ℃, 1.2kg _f.

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (11)

A polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated siloxane of Formula 1 and a polycarbonate block as recurring units; And polycarbonate,
The content of siloxane in the polysiloxane-polycarbonate copolymer is 15 to 30% by weight,
Wherein the content of siloxane in the total composition is 3 to 12 wt%
Polycarbonate resin composition:
[Chemical Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
m is independently an integer of 0 to 4,
n independently represents an integer of 2 to 1,000,
A represents a structure represented by the following formula (2) or (3)
(2)

In Formula 2,
Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group, or a substituted or unsubstituted alkylene group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group, A monocyclic or polycyclic arylene group having 6 to 30 carbon atoms,
(3)

In Formula 3,
R ₄ represents an aromatic or aromatic / aliphatic mixed hydrocarbon group having 6 to 30 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. The method according to claim 1,
Wherein the polycarbonate block contained as a repeating unit in the polysiloxane-polycarbonate copolymer is a polycarbonate block of the following formula:
[Chemical Formula 4]

In Formula 4,
R ₅ represents an aromatic hydrocarbon group substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or nitro, or an unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. The method according to claim 1,
Wherein the polysiloxane-polycarbonate copolymer has a viscosity average molecular weight of 10,000 to 70,000. The method according to claim 1,
Wherein the polycarbonate has a viscosity average molecular weight of 10,000 to 50,000. delete The method according to claim 1,
Wherein the weight ratio of polysiloxane-polycarbonate copolymer: polycarbonate is from 10:90 to 50:50. Reacting a hydroxy-terminated siloxane of Formula 1 with an oligomeric polycarbonate under an interfacial reaction condition to form a polysiloxane-polycarbonate intermediate;
Polymerizing the intermediate with a first polymerization catalyst to produce a polysiloxane-polycarbonate copolymer having a siloxane content of 15 to 30% by weight; And
Comprising mixing the polysiloxane-polycarbonate copolymer prepared with a polycarbonate.
A method for producing a polycarbonate resin composition having a siloxane content of 3 to 12% by weight in the whole composition:
[Chemical Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
m is independently an integer of 0 to 4,
n independently represents an integer of 2 to 1,000,
A represents a structure represented by the following formula (2) or (3)
(2)

In Formula 2,
Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group, or a substituted or unsubstituted alkylene group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group, A monocyclic or polycyclic arylene group having 6 to 30 carbon atoms,
(3)

In Formula 3,
R ₄ represents an aromatic or aromatic / aliphatic mixed hydrocarbon group having 6 to 30 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. 8. The method of claim 7,
Wherein the step of forming the intermediate comprises:
And mixing said hydroxy-terminated siloxane and said oligomeric polycarbonate in a weight ratio of 10:90 to 35:65. 8. The method of claim 7,
Wherein the step of forming the intermediate comprises:
Forming a mixture comprising the hydroxy-terminated siloxane and the oligomeric polycarbonate,
Wherein the mixture comprises a phase transfer catalyst, a molecular weight modifier and a second polymerization catalyst. 8. The method of claim 7,
Wherein the step of forming the intermediate comprises:
Forming a mixture comprising the hydroxy-terminated siloxane and the oligomeric polycarbonate; And
And then extracting the organic phase from the resulting mixture after the reaction of the hydroxy-terminated siloxane with the oligomeric polycarbonate is completed,
The step of polymerizing the intermediate,
Providing the first polymerization catalyst to the extracted organic phase. ≪ RTI ID = 0.0 > 21. < / RTI > 8. The method of claim 7,
Wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000.