TW201323519A - 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 method of manufacturing the same. More specifically, the present invention relates to a polycarbonate resin composition that comprises a polysiloxane-polycarbonate copolymer with high siloxane content and a polycarbonate in an appropriate mixing ratio, and thus has improved low-temperature impact resistance, flowability and heat resistance; and a method of manufacturing the same.

Description

Polycarbonate resin composition with improved low temperature impact resistance and method of producing the same

The present invention relates to a polycarbonate resin composition and a method of producing the same. More specifically, the present invention relates to a polycarbonate resin composition comprising a polyoxyalkylene-polycarbonate copolymer having a high decane content, and a polycarbonate having a suitable mixing ratio, and thus having Improved low temperature impact resistance, fluidity and heat resistance; and methods of making same.

Polycarbonate has good mechanical properties such as tensile strength, impact resistance, etc., and also has good dimensional stability, heat resistance and optical transparency. Therefore, it is widely used in various industries. However, although polycarbonate has good room temperature impact resistance, its impact resistance rapidly deteriorates at low temperatures.

A variety of copolymers have been investigated to improve this defect, and polyoxyalkylene-polycarbonate copolymers are known to have relatively good low temperature impact resistance. However, the currently used polyoxyalkylene-polycarbonate copolymers do not exhibit industrially satisfactory low temperature impact resistance. In addition, they often cause deterioration of other physical properties such as fluidity, heat resistance and the like.

Accordingly, there is a need to develop polycarbonate trees that exhibit significantly improved low temperature impact resistance while maintaining good polycarbonate inherent physical properties such as flowability, heat resistance, and the like. Fat composition.

[Previous Technical Literature]

[Patent Literature]

US 2003/0105226 A

The present invention is intended to solve the problems involved in the prior art described above. The technical object of the present invention is to provide a polycarbonate resin composition which exhibits remarkably improved low temperature impact resistance while maintaining good fluidity and heat resistance.

The present invention provides a polycarbonate resin composition comprising a polyoxyalkylene-polycarbonate copolymer and a polycarbonate, wherein the amount of the oxoxane in the polyoxyalkylene-polycarbonate copolymer is 10 to 35 wt%.

In another aspect, the present invention provides a method of preparing the polycarbonate resin composition, the method comprising: reacting a hydroxyl terminated methane with an oligomeric polycarbonate under interfacial reaction conditions to form a polyoxyl a step of an alkane-polycarbonate intermediate; a step of preparing the polyoxoxane-polycarbonate copolymer having an amount of 10 to 35 wt% of decane by polymerizing the intermediate product using a first polymerization catalyst; A step of mixing the prepared polyoxyalkylene-polycarbonate copolymer with a polycarbonate.

The polycarbonate resin composition according to the present invention can significantly improve low temperature impact resistance while ensuring good room temperature impact by including a polyoxyalkylene-polycarbonate copolymer having a specific decane content and a polycarbonate. Resistance, fluidity, and heat resistance, and thus can be suitably used in various applications such as helmets, automobile parts, mobile phone cases, and the like.

[Mode of the invention]

The invention will be more specifically disclosed hereinafter. The objects, features, and advantages of the present invention will be more readily understood from the embodiments described herein. The invention is not limited to the specific embodiments described herein, and may be embodied in other forms. The specific embodiments described herein are provided to provide a complete and complete disclosure of the disclosure and the disclosure of the invention. Therefore, the invention is not limited to the specific embodiments described below.

The term "reaction product" as used herein means a substance formed by the reaction of two or more reactants.

Further, although the terms "first", "second", and the like are used herein to describe the polymerization catalyst, the polymerization catalysts are not limited to these terms. These terms are only used to distinguish one another from their polymerization catalysts. For example, the first polymerization catalyst and the second polymerization catalyst may be the same type of catalyst or different types of catalyst.

Further, in the chemical formula disclosed herein, although the English letter "R" for indicating hydrogen, a halogen atom and/or a hydrocarbon group has a numerical subscript, "R" is not limited to this subscript. "R" independently represents hydrogen, a halogen atom, and/or a hydrocarbon group. For example, even if two or more "R" systems have the same numerical subscript, the "R" may represent the same hydrocarbyl group or a different hydrocarbyl group. Also, even if two or more "R" systems have different numerical subscripts, the "R" may represent the same hydrocarbon group or a different hydrocarbon group.

[Polycarbonate resin composition]

The polycarbonate composition according to the present invention comprises a polyoxyalkylene-polycarbonate copolymer and a polycarbonate, wherein the amount of the oxoxane in the polyoxyalkylene-polycarbonate copolymer is 10 to 35 by weight. %.

Polyoxane-polycarbonate copolymer (Si-PC)

The polyoxyalkylene-polycarbonate copolymer contained in the polycarbonate composition of the present invention may comprise the following repeating unit: a hydroxy-terminated oxime of the following Chemical Formula 1a or Chemical Formula 1; and the polymerization of the following Chemical Formula 4 Carbonate block:

In the above Chemical Formula 1a, R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, an alkoxy group or an aryl group having 1 to 20 carbon atoms. 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 a methyl group, an ethyl group or a propyl group. Further, for example, the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as a methoxy group, an ethoxy group or a propoxy group, and the aryl group may have 6 to 10 An aryl group of a carbon atom such as a phenyl group, a chlorophenyl group or a tolyl group.

R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group. For example, R ₂ may be an alkyl or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or an alkenyloxy group having 2 to 13 carbon atoms, and a ring having 3 to 6 carbon atoms. An alkyl or cycloalkoxy group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group or an aralkyloxy group having 7 to 13 carbon atoms, or an alkane having 7 to 13 carbon atoms Aryl or alkaryloxy.

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

The subscript "m" is an integer representing 0 to 4 independently.

The subscript "n" is an integer representing from 2 to 1,000, preferably from 2 to 500, more preferably from 5 to 100.

In one embodiment, as the hydroxy-terminated oxime of Formula 1a, a oxoxane monomer available from Dow Corning can be used ( ), but it is not limited to this.

In the above Chemical Formula 1, R ₁ , R ₂ , R ₃ , m and n are the same as defined in the above Chemical Formula 1a, and "A" represents the structure of the following Chemical Formula 2 or 3.

In the above Chemical Formula 2, X represents Y or NH-Y-NH, wherein Y represents a linear or branched aliphatic group having 1 to 20 carbon atoms, and a cycloalkyl group (for example, a cycloalkyl group of 3 to 6 carbon atoms), or a monocyclic or polycyclic ring having 6 to 30 carbon atoms which is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. Yan Fangji. For example, Y may be an aliphatic group which is unsubstituted or substituted with a halogen atom, an aliphatic group containing an oxygen, nitrogen or sulfur atom in its main chain, or may be derived from bisphenol A, resorcin, hydrogen An aryl group derived from hydrazine or diphenylphenol. For example, Y can be represented by one of the following Chemical Formulas 2a to 2h.

In the above Chemical Formula 3, R ₄ represents an aromatic hydrocarbon group or an aromatic/aliphatic mixed hydrocarbon group having 6 to 30 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. R ₄ may have a structure containing a halogen, oxygen, nitrogen or sulfur as well as a carbon atom. For example, R ₄ may be phenyl, chlorophenyl or tolyl (preferably phenyl).

In one embodiment, the hydroxy-terminated oxime of Formula 1 may be the reaction product of the hydroxy-terminated oxirane of the above Chemical Formula 1a and a mercapto compound.

The mercapto compound may have, for example, an aromatic structure, an aliphatic structure, or a mixed structure comprising both an aromatic form and an aliphatic form. When the mercapto compound is an aromatic structure or a mixed structure, it may have 6 to 30 carbon atoms, and when the mercapto compound is an aliphatic structure, it may have 1 to 20 carbon atoms. The mercapto compound may further comprise a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated oxime of the above formula 1 may be the reaction product of the hydroxy-terminated oxirane of the above formula 1a and a diisocyanate compound.

The diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate or 4,4'-methylene diphenyl diisocyanate.

In another embodiment, the hydroxy-terminated oxime of the above formula 1 may be the reaction product of a hydroxy-terminated oxirane of the above formula 1a and a phosphorus-containing compound (aromatic or aliphatic phosphate compound).

The phosphorus-containing compound may have the structure of the following chemical formula 1b.

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

Preferably, the polyoxyalkylene-polycarbonate copolymer comprises the following repeating unit: the hydroxy-terminated oxime of the above Chemical Formula 1a or Chemical Formula 1; and the polycarbonate block of the following Chemical Formula 4,

In the above formula 4, R ₅ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which is unsubstituted or has an alkyl group having 1 to 20 carbon atoms (for example, 1 to An alkyl group of 13 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (for example, an alkenyl group having 2 to 13 carbon atoms) An alkoxy group (for example, an alkoxy group having 1 to 13 carbon atoms), a halogen atom or a nitro group.

The aromatic hydrocarbon group may be derived from a compound of the following chemical formula 4a.

In the above chemical formula 4a, X represents an alkylene group; a linear, branched or cyclic alkyl group having no functional group; or a functional group (such as a thioether, an ether, an anthracene, an anthracene, a ketone, a naphthyl group, an isobutylphenyl group) Or a straight chain, a branched chain or a cyclic alkyl group. Preferably, X may be a linear or branched alkyl group having 1 to 10 carbon atoms or a cyclic alkyl group having 3 to 6 carbon atoms.

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

The subscripts "n" and "m" are independent integers from 0 to 4.

The compound of the above formula 4a may be, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4- Hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxybenzene) Ethylene, 1,10-bis(4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl) ) propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2, 2-bis(4-hydroxyphenyl)decane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 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)methane, between Hydroquinone, hydroquinone, 4,4'-dihydroxyphenyl ether [bis(4-hydroxyphenyl)ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4, 4'-dihydroxy-3,3'-dichlorodiphenyl ether, bis(3,5-dimethyl-4-hydroxyphenyl) , bis(3,5-dichloro-4-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 Bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-double (3 , 5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl)butane, 1,4-double ( 4-hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-di Methyl-4-hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4- Hydroxyphenyl)-2-methyl-butane, 4,4'-dihydroxydiphenyl sulfide [bis(4-hydroxyphenyl)fluorene], bis(3,5-dimethyl-4-hydroxybenzene) , bis(3-chloro-4-hydroxyphenyl) fluorene, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl)arene, bis(3-methyl-4-hydroxyl) Phenyl) sulfide, bis(3,5-dimethyl-4-hydroxyphenyl) sulfide, bis(3,5-dibromo-4-hydroxyphenyl)arene, 4,4'-dihydroxy Diphenyl ketone, 3,3', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxybiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxy Naphthalene, but it is not limited thereto. Among them, one of the representative ones is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional bishydroxyphenols are described in U.S. Patent Nos. 2,999,835, 3,028,365, 3,153,008, and 3,334,154. The above bishydroxyphenols may be used singly or in combination of two or more thereof.

In the case of a carbonate precursor, for example, carbon ruthenium chloride (phosgene), carbon ruthenium bromide, dihaloformate, diphenyl carbonate, dimethyl carbonate, or the like can be used as the polycarbonate resin. Another monomer, but it is not limited thereto.

In the polycarbonate resin composition of the present invention, the amount of the siloxane in the polyoxyalkylene-polycarbonate copolymer is 10 to 35% by weight, preferably 15 to 30% by weight, and more preferably 20 Up to 30% by weight. Based on the total weight of the copolymer, if the amount of helium oxide is Below 10% by weight, the improvement effect of low-temperature impact resistance may be insufficient as compared with the demand of the present invention. If the amount of the decane exceeds 35% by weight, the amount of the polycarbonate in the copolymer is relatively lowered, and thus physical properties such as fluidity, heat resistance, room temperature impact resistance, transparency, and the like may be deteriorated.

Preferably, the polyoxyalkylene-polycarbonate copolymer may have a viscosity average molecular weight (Mv) of from 10,000 to 70,000, more preferably from 15,000 to 30,000. If the copolymer has a viscosity average molecular weight of less than 10,000, its mechanical properties may be seriously deteriorated. If the viscosity average molecular weight exceeds 70,000, the melt viscosity thereof increases, and thus there may be a problem in resin processing.

Polycarbonate (PC)

The polycarbonate which is contained in the polycarbonate composition of the present invention together with the polyoxyalkylene-polycarbonate copolymer is not particularly limited. Any conventional polycarbonate resin can be used.

Preferably, the polycarbonate has a viscosity average molecular weight of from 10,000 to 50,000, more preferably from 15,000 to 35,000. If the polycarbonate has a viscosity average molecular weight of less than 10,000, its mechanical properties may be seriously deteriorated. If the viscosity average molecular weight is more than 50,000, the fluidity is lowered, and thus there may be a problem in resin processing.

In the polycarbonate composition of the present invention, the weight of the polyoxyalkylene-polycarbonate copolymer and the polycarbonate is preferably from 10:90 to 50:50, more preferably from 15:85 to 40:60. If the weight ratio of the copolymer to the polycarbonate is less than 10:90, the improvement effect of low temperature impact resistance may be insufficient as compared with the demand of the present invention. If the weight ratio is more than 50:50, physical properties such as fluidity, heat resistance, room temperature impact resistance, transparency, and the like may be deteriorated.

The invention comprising both a polyoxyalkylene-polycarbonate copolymer and a polycarbonate The amount of the decane in the polycarbonate resin composition is preferably from 3 to 12% by weight, more preferably from 4 to 10% by weight. When the amount of the decane in the total composition is in the range of from 3 to 12% by weight, the low-temperature impact resistance can be remarkably improved (more than twice) while ensuring good fluidity and room temperature impact resistance. Sex.

[Method of preparing the polycarbonate resin composition]

The polycarbonate composition of the present invention can be prepared by reacting a hydroxy-terminated oxime with an oligomeric polycarbonate under interfacial reaction conditions consisting of an aqueous alkaline solution and an organic phase to form a poly a oxoxane-polycarbonate intermediate; polymerizing the intermediate product by using a first polymerization catalyst to prepare a polyoxyalkylene-polycarbonate copolymer; and, the prepared polyoxyalkylene-polycarbonate The ester copolymer is mixed with a polycarbonate.

In a preferred embodiment, the step of forming the intermediate product can comprise the hydroxyl terminated methane oxide and the oligomeric polycarbonate from 10:90 to 35:65 (more preferably 15: 85 to 30:70) The step of mixing the weight ratio. If the mixing ratio of the hydroxy-terminated oxiranane is less than 10, the improved effect of low-temperature impact resistance may be insufficient as compared with the demand of the present invention. If the mixing ratio of the hydroxy-terminated oxirane is more than 35, the amount of the polycarbonate in the copolymer is relatively lowered, and thus physical properties such as fluidity, heat resistance, room temperature impact resistance, transparency, and the like may be deteriorated.

The polycarbonate used in the preparation of the polyoxyalkylene-polycarbonate copolymer may be an oligomeric polycarbonate having a viscosity average molecular weight of from 800 to 20,000, more preferably from 1,000 to 15,000. If the oligomeric polycarbonate has a viscosity average molecular weight of less than 800, its molecular weight distribution may become broad and its physical properties may deteriorate. If the oligomeric polycarbonate has a viscosity average molecular weight of more than 20,000, its reactivity may be lowered.

In one embodiment, the oligomeric polycarbonate can be prepared by adding the above-described bishydroxyphenol compound to an aqueous alkaline solution to bring it into a phenolate state, and then to the phenolate state. The phenol compound is added to dichloromethane containing the injected phosgene to carry out the reaction. To prepare the oligomer, it is preferred to maintain the molar ratio of phosgene to bisphenol in the range of from about 1:1 to 1.5:1, and more preferably from 1:1 to 1.2:1. If the molar ratio of phosgene to bisphenol is less than 1, the reactivity may be lowered. If the molar ratio of phosgene to bisphenol is more than 1.5, the molecular weight thereof excessively increases, and thus the workability may be lowered.

The above reaction for forming an oligomer can be usually carried out at a temperature ranging from about 15 to 60 °C. To adjust the pH of the reaction mixture, an alkali metal hydroxide (for example, sodium hydroxide) can be used.

In one embodiment, the step of forming the intermediate product comprises the step of forming a mixture comprising the hydroxyl terminated azide and the oligomeric polycarbonate, wherein the mixture may comprise a phase transfer catalyst a molecular weight controlling agent and a second polymerization catalyst. Furthermore, the step of forming the intermediate product may comprise the step of forming a mixture comprising the hydroxyl terminated azide and the oligomeric polycarbonate; and the hydroxyl terminated paraxane and the oligomer After the polycarbonate reaction is completed, the step of extracting the organic phase from the obtained mixture, wherein the step of polymerizing the intermediate product may include the step of supplying the first polymerization catalyst to the extracted organic phase.

Specifically, the polyoxyalkylene-polycarbonate copolymer can be prepared by adding the above-described hydroxy-terminated decane of Chemical Formula 1a or Chemical Formula 1 to a mixture of an organic phase/aqueous phase containing the polycarbonate. And, subsequently, the molecular weight controlling agent and the catalyst are fed.

As the molecular weight controlling agent, a monofunctional compound similar to that used in the preparation of polycarbonate can be used. The monofunctional compound can be, for example, a phenol-based derivative such as p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, and p-isoindole. A phenol, or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) is used.

A polymerization catalyst and/or a phase transfer catalyst can be used as the catalyst. The polymerization catalyst may be, for example, triethylamine (TEA), and the phase transfer catalyst may be a compound of the following Chemical Formula 5.

[Chemical Formula 5] (R ₇ ) ₄ Q ⁺ X ^-

In the above 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 , wherein R ₈ represents a hydrogen atom and has An alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 18 carbon atoms.

Specifically, the phase transfer catalyst may be, 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 or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX, wherein 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 amount of the phase transfer catalyst is preferably from about 0.01 to 10% by weight, and more preferably from 0.1 to 10% by weight, based on the total weight of the hydroxy-terminated oxime and the oligomeric polycarbonate. If the amount of the phase transfer catalyst is less than 0.01% by weight, the reactivity may be lowered. The amount of the phase transfer catalyst is more than 10% by weight, and precipitation may occur or penetrate The brightness may deteriorate.

In one embodiment, after preparing the polyoxyalkylene-polycarbonate copolymer, the organic phase dispersed in dichloromethane is washed with a base and subsequently separated. Next, the organic phase was washed with a 0.1 N hydrochloric acid solution, followed by rinsing twice or three times with distilled water. After the completion of the rinsing, the concentration of the organic phase dispersed in dichloromethane is continuously adjusted, and granulation is carried out by using a constant amount of pure water at 30 to 100 ° C, preferably 60 to 80 ° C. If the temperature of the pure water is lower than 30 ° C, the granulation rate is slow, and therefore, the granulation time may be too long. If the temperature of the pure water is higher than 100 ° C, it may be difficult to obtain a polycarbonate having a uniform size and morphology. After the granulation is completed, the product is preferably dried at 100 to 120 ° C for 5 to 10 hours. More preferably, the product is first dried at 100 to 110 ° C for 5 to 10 hours, followed by drying at 110 to 120 ° C for 5 to 10 hours.

The method of mixing the prepared polyoxyalkylene-polycarbonate copolymer and polycarbonate is not particularly limited. Preferably, the polyoxyalkylene-polycarbonate copolymer and the polycarbonate are mixed in 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 hydroxyl terminated azide>

0.0666 mol (mol) of monomer (BY16-799, Dow Corning) was dissolved in 100 ml (mL) of benzene under nitrogen atmosphere, and 6.66 mmol (mmol) of 1,4-diazabicyclo was added. [2, 2, 2] octane. To the reflux of the resulting solution, 0.0333 mol of 4,4-methylenebis(phenyl isocyanate) dissolved in 200 mL of benzene was slowly added thereto (1 hour). The resulting solution was refluxed for 12 hours. After the reaction is completed, the solvent is removed from the solution, and the resulting product is dissolved in acetone, washed with hot distilled water, and It was dried in a vacuum oven for 24 hours to prepare a hydroxy-terminated oxime having a urethane chain of the following Chemical Formula 6. The synthesis was confirmed by H-NMR analysis in which the hydrogen atom peak of the first carbon atom bonded to the aliphatic chain adjacent to the terminal phenyl group was observed at 2.75 ppm in the following Chemical Formula 6.

<Preparation of polyoxyalkylene-polycarbonate copolymer>

The interfacial reaction of bisphenol A with phosgene in the aqueous phase was carried out in the presence of dichloromethane to prepare 400 mL of oligomeric polycarbonate having a viscosity average molecular weight of about 1,000. In the obtained oligomerized polycarbonate mixture, 20% by weight of a hydroxyl group-terminated oxirane having a urethane chain of Chemical Formula 6 dissolved in dichloromethane, 1.8 mL of chlorinated tetrachloride Butylammonium (TBACl), 1.5 g of p-tert-butylphenol (PTBP) was mixed with 275 microliters (μL) of triethylamine (TEA, 15 wt% solution) and reacted for 30 minutes. The oligomerized polycarbonate mixture after standing reaction is allowed to phase separate. After the phase separation, only the organic phase was collected, and 170 g of a sodium hydroxide solution, 370 g of dichloromethane, and 300 μL of triethylamine (15 wt% solution) were mixed thereto, and reacted for 2 hours. After phase separation, the organic phase with increased viscosity is washed with a base and separated. Thereafter, the obtained organic phase was washed with a 0.1 N hydrochloric acid solution, and then washed 2 to 3 times with distilled water. After the completion of the rinsing, the concentration of the organic phase was continuously adjusted, and then granulation was carried out at 76 ° C by using a constant amount of pure water. After the granulation was completed, the product was first dried at 110 ° C for 8 hours and then dried at 120 ° C for 10 hours. The synthesis was confirmed by H-NMR analysis, wherein the methylene peak of the polyoxyalkylene was observed at 2.65 ppm, the peak of the methoxy group was observed at 3.85 ppm, and the hydrogen peak of the benzene ring was at 7.1 to 7.5 Observed in ppm.

<Preparation of polycarbonate resin composition>

A polycarbonate resin composition was prepared by mixing the prepared polyoxyalkylene-polycarbonate copolymer with polycarbonate (3022 PJ, Mv: 21,000, Samyang Corporation) in a weight ratio of 40:60. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Example 2

<Preparation of hydroxyl terminated azide>

0.4 mol of monomer (BY16-799, Dow Corning) was dissolved in 300 mL of chloroform in a 500 mL three-necked flask equipped with a condenser under nitrogen atmosphere, followed by 67 mL of triethylamine (TEA) catalyst. Join it. 0.2 mol of terephthalic acid chloride (TCL) dissolved in 1,000 mL of chloroform was slowly added thereto under reflux of the resulting solution for 1 hour, and the resulting solution was refluxed for 12 hours. After the reaction was completed, the solvent was removed from the solution, and the product was dissolved in acetone, washed with hot distilled water, and dried in a vacuum oven for 24 hours to prepare a hydroxyl-terminated oxime having an ester chain of the following Chemical Formula 7. alkyl. The synthesis was confirmed by H-NMR analysis. The methylene peak of the polyoxyalkylene was observed at 2.6 ppm, and the hydrogen peak of the benzene ring of TCL was observed at 8.35 ppm, and the benzene ring of the polyoxyalkylene was observed. The hydrogen peak was observed at 6.75 to 7.35 ppm.

<Preparation of polyoxyalkylene-polycarbonate copolymer>

The interfacial reaction of bisphenol A with phosgene in the aqueous phase is carried out in the presence of methylene chloride to prepare 400 mL of oligomers having a viscosity average molecular weight of about 1,000. Polycarbonate mixture. In the obtained oligomerized polycarbonate mixture, 30% by weight of a hydroxyl group-terminated hydroxy alkane having an ester chain of Chemical Formula 7 and 1.8 mL of tetrabutylammonium chloride (TBACl) dissolved in dichloromethane 1.5 g of p-tert-butylphenol (PTBP) was mixed with 275 μL of triethylamine (TEA, 15 wt% aqueous solution) and reacted for 30 minutes. The reacted oligomeric polycarbonate mixture is allowed to stand for phase separation. After the phase separation, only the organic phase was collected, and 170 g of an aqueous sodium hydroxide solution, 360 g of dichloromethane, and 300 μL of triethylamine (15 wt% aqueous solution) were mixed thereinto, and reacted for 2 hours. After phase separation, the organic phase with increased viscosity is washed with a base and separated. Thereafter, the resulting organic phase was washed with a 0.1 N hydrochloric acid solution, followed by rinsing with distilled water for 2 to 3 times. After the completion of the rinsing, the concentration of the organic phase was continuously adjusted, and granulation was carried out at 76 ° C by using a constant amount of pure water. After the granulation was completed, the product was first dried at 110 ° C for 8 hours and then dried at 120 ° C for 10 hours. The synthesis of the copolymer was confirmed by H-NMR analysis, wherein the methylene peak of the polyoxyalkylene was observed at 2.6 ppm and 2.65 ppm, and the hydrogen peak of the benzene ring of TCL was observed at 8.35 ppm. The hydrogen peak of the benzene ring of the polyoxyalkylene was observed at 6.95 to 7.5 ppm.

<Preparation of polycarbonate resin composition>

A polycarbonate resin composition was prepared by mixing a polysiloxane-polycarbonate copolymer prepared by a weight ratio of 20:80 with polycarbonate (3022 PJ, Mv: 21,000, Samyang Corporation). The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Example 3

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that 20% by weight of the hydroxy-terminated oxime of the above Chemical Formula 7 was used to prepare the polyoxyalkylene-polycarbonate copolymer, and Prepared by mixing in a weight ratio of 30:70 Polysiloxane-polycarbonate copolymer and polycarbonate (3027PJ, Mv: 24, 600, Samyang Corporation). The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Example 4

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that 20% by weight of a hydroxy-terminated oxime of the following Chemical Formula 8 was used to prepare the polyoxyalkylene-polycarbonate copolymer. The prepared polyoxyalkylene-polycarbonate copolymer and polycarbonate (3022 PJ, Mv: 21,000, Samyang Corporation) were mixed at a weight ratio of 30:70. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Example 5

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that 30% by weight of the hydroxy-terminated oxime of the above Chemical Formula 8 was used to prepare the polyoxyalkylene-polycarbonate copolymer, and The prepared polyoxyalkylene-polycarbonate copolymer and polycarbonate (3022 PJ, Mv: 21,000, Samyang Corporation) were mixed at a weight ratio of 15:85. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 1

The polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that the polyoxyalkylene-polycarbonate copolymer was prepared using 8% by weight of the hydroxy-terminated oxime of the above Chemical Formula 7, and Prepared by mixing in a weight ratio of 60:40 Polysiloxane-polycarbonate copolymer and polycarbonate (3022PJ, Mv: 21,000, Samyang Corporation). The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 2

The polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that the polyoxyalkylene-polycarbonate copolymer was prepared using 9% by weight of the hydroxy-terminated oxime of the above Chemical Formula 8, and The prepared polyoxyalkylene-polycarbonate copolymer and polycarbonate (3027PJ, Mv: 24, 600, Samyang Corporation) were mixed at a weight ratio of 30:70. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 3

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that 45% by weight of the hydroxy-terminated oxime of the above Chemical Formula 8 was used to prepare the polyoxyalkylene-polycarbonate copolymer, and The prepared polyoxyalkylene-polycarbonate copolymer and polycarbonate (3027PJ, Mv: 24, 600, Samyang Corporation) were mixed at a weight ratio of 40:60. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below. The composition of Comparative Example 3 could not be molded by injection, and therefore it was not able to measure its low temperature impact resistance.

Comparative Example 4

The polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that the polyoxyalkylene-polycarbonate copolymer was prepared using 8% by weight of the hydroxy-terminated oxime of the above Chemical Formula 7, and Only the prepared polyoxyalkylene-polycarbonate copolymer was used without mixing with the polycarbonate. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 5

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that 20% by weight of the hydroxy-terminated oxime of the above Chemical Formula 7 was used to prepare the polyoxyalkylene-polycarbonate copolymer, and Only the prepared polyoxyalkylene-polycarbonate copolymer was used without mixing with the polycarbonate. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 6

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that only polycarbonate (3022 PJ, Mv: 21,000, Samyang Corporation) was used without using any polyoxyalkylene-polycarbonate copolymer. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

Comparative Example 7

A polycarbonate resin composition was prepared by the same method as disclosed in Example 1, except that only polycarbonate (3030 PJ, Mv: 31, 200, Samyang Corporation) was used without using any polyoxyalkylene-polycarbonate copolymer. The physical properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.

As shown in Table 1 above, the polycarbonate resin composition prepared according to the examples showed better room temperature impact resistance and fluidity, and was significantly superior as compared with the polycarbonate resin composition prepared according to the comparative examples. Low temperature impact resistance.

The methods for measuring the above characteristics used in the examples and comparative examples are as follows.

(a) H-NMR (nuclear magnetic resonance spectroscopy): This analysis was carried out using Avance DRX 300 (Bruker).

(b) Viscosity average molecular weight (Mv): The viscosity of the dichloromethane solution was measured at 20 ° C using an Ubbelohde viscometer, and its ultimate viscosity [η] was calculated according to the following equation.

[η]=1.23×10 ^-5 Mv ^0.83

(c) Impact resistance: Impact resistance was measured at room temperature to 50 ° C using an impact test machine (RESIL IMPACTOR, CEAST Co., Ltd.).

(d) MI (melt index): The melt index indicates the flow at a specific temperature and load, which was measured at 300 ° C under a load of 1.2 kg _f according to ASTM D1238.

The invention has been disclosed with reference to specific embodiments. It is to be understood by those skilled in the art that the present invention may be modified without departing from the spirit and scope of the invention. Accordingly, the disclosed embodiments are to be considered as illustrative and not restrict The scope of the present invention is not to be construed as being limited by the foregoing description, and the scope of the invention is intended to be included in the scope of the appended claims.

Claims (11)

A polycarbonate resin composition comprising a polyoxyalkylene-polycarbonate copolymer and a polycarbonate, wherein the amount of the oxoxane in the polyoxyalkylene-polycarbonate copolymer is 10 to 35 by weight %. The composition according to claim 1, wherein the polyoxyalkylene-polycarbonate copolymer comprises the following repeating unit: a hydroxy-terminated oxime of the following Chemical Formula 1a or Chemical Formula 1; The polycarbonate block of Chemical Formula 4, Wherein, in the chemical formula 1a, R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, an alkoxy group or an aryl group having 1 to 20 carbon atoms; and the R ₂ group independently represents 1 to 13 a hydrocarbon group of a carbon atom, or a hydroxyl group; R ₃ independently represents an alkylene group having 2 to 8 carbon atoms; m is an integer representing an integer of 0 to 4; and n is an integer of 2 to 1,000; Wherein, in Chemical Formula 1, R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group, an alkoxy group or an aryl group having 1 to 20 carbon atoms; and R ₂ is independently represented by having 1 to 13 a hydrocarbon group of a carbon atom, or a hydroxyl group; R ₃ independently represents an alkylene group having 2 to 8 carbon atoms; m is independently an integer of 0 to 4; n is an integer representing an integer of 2 to 1,000; and A is an Indicates the structure of the following chemical formula 2 or 3: Wherein, in Chemical Formula 2, X-form Y or NH-Y-NH, wherein Y-form represents a straight-chain or branched-chain aliphatic group having 1 to 20 carbon atoms, a cycloalkyl group, or 6 to a monocyclic or polycyclic extended aryl group having 30 carbon atoms and which is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; Wherein, in Chemical Formula 3, R ₄ represents an aromatic hydrocarbon group or an aromatic/aliphatic mixed hydrocarbon group having 6 to 30 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms; Wherein, in Chemical Formula 4, R ₅ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms which is unsubstituted or substituted by an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or a nitro group. Replace. The composition of claim 1, wherein the polyoxyalkylene-polycarbonate copolymer has a viscosity average molecular weight of 10,000 to 70,000. The composition of claim 1, wherein the polycarbonate has a viscosity average molecular weight of 10,000 to 50,000. The composition of claim 1, wherein the amount of the oxoxane in the total composition is from 3 to 12% by weight. The composition of claim 1, wherein the weight ratio of the polyoxyalkylene-polycarbonate copolymer to the polycarbonate is from 10:90 to 50:50. A method for preparing a polycarbonate resin composition according to claim 1, wherein the method comprises: reacting a hydroxy-terminated siloxane with an oligomeric polycarbonate under interfacial reaction conditions to form a poly a step of preparing a oxoxane-polycarbonate intermediate; a step of preparing the polyoxoxane-polycarbonate copolymer having an amount of 10 to 35 wt% of decane by polymerizing the intermediate product using a first polymerization catalyst And a step of mixing the prepared polyoxyalkylene-polycarbonate copolymer with polycarbonate. The method for preparing a composition according to claim 7, wherein the step of forming the intermediate product comprises: the hydroxyl-terminated helioxane in a weight ratio of 10:90 to 35:65; The step of mixing the oligomeric polycarbonate. The method for preparing a composition according to claim 7, wherein the step of forming the intermediate product comprises: forming a mixture comprising the hydroxyl terminated azide and the oligomerized polycarbonate. And a step of, wherein the mixture comprises a phase transfer catalyst, a molecular weight controlling agent, and a second polymerization catalyst. The method of preparing a composition according to claim 7, wherein the step of forming the intermediate product comprises the step of forming a mixture comprising the hydroxyl terminated azide and the oligomerized polycarbonate. And the step of extracting the organic phase from the resulting mixture after the completion of the reaction of the hydroxyl terminated azide with the oligomeric polycarbonate, and wherein the step of polymerizing the intermediate product comprises: A polymerization catalyst is provided to the extracted organic phase. The method of preparing a composition according to claim 7, wherein the oligomerized polycarbonate has a viscosity average molecular weight of 800 to 20,000.