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WO2013066000A1 - Composition de résine de polycarbonate ayant une résistance au choc améliorée à basse température et son procédé de fabrication - Google Patents

Composition de résine de polycarbonate ayant une résistance au choc améliorée à basse température et son procédé de fabrication Download PDF

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Publication number
WO2013066000A1
WO2013066000A1 PCT/KR2012/008834 KR2012008834W WO2013066000A1 WO 2013066000 A1 WO2013066000 A1 WO 2013066000A1 KR 2012008834 W KR2012008834 W KR 2012008834W WO 2013066000 A1 WO2013066000 A1 WO 2013066000A1
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Prior art keywords
polycarbonate
group
chemical formula
carbon atoms
polysiloxane
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PCT/KR2012/008834
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English (en)
Inventor
Yun Ju Chang
Kyung Moo Shin
Hong Chol RHEE
Jae Hyun Kim
Sun Chul JIN
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Samyang Corporation
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Publication of WO2013066000A1 publication Critical patent/WO2013066000A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • 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.
  • Polycarbonate has good mechanical properties such as tensile strength, impact resistance, etc. and also has good dimensional stability, heat resistance and optical transparency. Thus, it has been extensively used in many industries. However, although polycarbonate has good impact resistance at room temperature, its impact resistance rapidly becomes worse at low temperature.
  • polysiloxane-polycarbonate copolymer has relatively good impact resistance at low temperature.
  • polysiloxane-polycarbonate copolymers that are currently used conventionally do not show industrially satisfactory low-temperature impact resistance.
  • they often cause deterioration in other physical properties such as flowability, heat resistance, etc.
  • the present invention is intended to solve the problems involved in the prior arts as stated above.
  • the technical purpose of the present invention is to provide a polycarbonate resin composition which shows significantly improved low-temperature impact resistance while maintaining good flowability and heat resistance.
  • the present invention provides a polycarbonate resin composition comprising a polysiloxane-polycarbonate copolymer and a polycarbonate, wherein the amount of siloxane in the polysiloxane-polycarbonate copolymer is 10 to 35% by weight.
  • the present invention provides a method for preparing the polycarbonate resin composition, the method comprising: a step of reacting hydroxy-terminated siloxane and oligomeric polycarbonate under an interfacial reaction condition to form a polysiloxane-polycarbonate intermediate; a step of polymerizing the intermediate by using a first polymerization catalyst to prepare a polysiloxane-polycarbonate copolymer having a siloxane amount of 10 to 35% by weight; and a step of mixing the prepared polysiloxane-polycarbonate copolymer and a polycarbonate.
  • the polycarbonate resin composition according to the present invention can improve low-temperature impact resistance significantly while securing good impact resistance at room temperature, flowability and heat resistance, and thus can be used properly in various applications such as helmet, automobile parts, cell phone housing, etc.
  • reaction product means a substance that is formed by reacting two or more reactants.
  • first,” “second” and the like are used herein for the description of polymerization catalysts, the polymerization catalysts are not limited by these terms. These terms are just used to distinguish the polymerization catalysts from each other.
  • a first polymerization catalyst and a second polymerization catalyst may be of the same kind of catalyst or different kinds of catalyst.
  • R is not limited by such a subscript.
  • R independently represents hydrogen, halogen atom and/or hydrocarbon group, etc.
  • R may represent the same hydrocarbon group or different hydrocarbon groups.
  • R may represent the same hydrocarbon group or different hydrocarbon groups.
  • the polycarbonate resin composition according to the present invention comprises a polysiloxane-polycarbonate copolymer and a polycarbonate, wherein the amount of siloxane in the polysiloxane-polycarbonate copolymer is 10 to 35% by weight.
  • Si-PC P olysiloxane-polycarbonate copolymer
  • the polysiloxane-polycarbonate copolymer comprised in the polycarbonate resin composition of the present invention may comprise, as repeating units, a hydroxy-terminated siloxane of the following chemical formula 1a or chemical formula 1; and a polycarbonate block of the following chemical formula 4:
  • R 1 independently represents hydrogen atom, halogen atom, hydroxy group, or alkyl group, alkoxy group or aryl group having 1 to 20 carbon atoms.
  • the halogen atom may be Cl or Br
  • the alkyl group may be an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl or propyl group.
  • the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms such as methoxy, ethoxy or propoxy group
  • the aryl group may be an aryl group having 6 to 10 carbon atoms such as phenyl, chlorophenyl or tolyl group.
  • R 2 independently represents hydrocarbon group having 1 to 13 carbon atoms or hydroxy group.
  • R 2 may be alkyl or alkoxy group having 1 to 13 carbon atoms, alkenyl or alkenyloxy group having 2 to 13 carbon atoms, cycloalkyl or cycloalkoxy group having 3 to 6 carbon atoms, aryloxy group having 6 to 10 carbon atoms, aralkyl or aralkoxy group having 7 to 13 carbon atoms, or alkaryl or alkaryloxy group having 7 to 13 carbon atoms.
  • R 3 independently represents alkylene group having 2 to 8 carbon atoms.
  • n independently represents an integer of 2 to 1,000, preferably 2 to 500, and more preferably 5 to 100.
  • a siloxane monomer available from Dow Corning ( ) may be used, but it is not limited thereto.
  • R 1 , R 2 , R 3 , m and n are the same as defined in chemical formula 1a above, and “A” represents a structure of the following chemical formula 2 or 3.
  • X represents Y or NH-Y-NH, wherein Y represents linear or branched aliphatic group having 1 to 20 carbon atoms, cycloalkylene group (for example, cycloalkylene group having 3 to 6 carbon atoms), or mono- or polycyclic arylene group having 6 to 30 carbon atoms and being unsubstituted or substituted with halogen atom, alkyl group, alkoxy group, aryl group or carboxyl group.
  • Y represents linear or branched aliphatic group having 1 to 20 carbon atoms, cycloalkylene group (for example, cycloalkylene group having 3 to 6 carbon atoms), or mono- or polycyclic arylene group having 6 to 30 carbon atoms and being unsubstituted or substituted with halogen atom, alkyl group, alkoxy group, aryl group or carboxyl group.
  • Y may be an aliphatic group that is unsubstituted or substituted with halogen atom, an aliphatic group that contains oxygen, nitrogen or sulfur atom in its main chain, or an arylene group that can be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol.
  • Y can be represented, for example, by one of the following chemical formulas 2a to 2h.
  • R 4 represents an aromatic hydrocarbon group or aromatic/aliphatic mixed-type 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 halogen, oxygen, nitrogen or sulfur as well as carbon atom(s).
  • R 4 may be phenyl, chlorophenyl or tolyl (preferably, phenyl).
  • the hydroxy-terminated siloxane of chemical formula 1 may be a reaction product of a hydroxy-terminated siloxane of the above chemical formula 1a and an acyl compound.
  • the acyl compound may have, for example, an aromatic structure, an aliphatic structure, or a mixed type structure comprising both aromatic and aliphatic forms.
  • the acyl compound When the acyl compound is of an aromatic structure or a mixed type structure, it can have 6 to 30 carbon atoms, and when the acyl compound is of an aliphatic structure, it can have 1 to 20 carbon atoms.
  • the acyl compound may further comprise halogen, oxygen, nitrogen or sulfur atom.
  • the hydroxy-terminated siloxane of the above chemical formula 1 may be a reaction product of a hydroxy-terminated siloxane of the above chemical formula 1a and a diisocyanate compound.
  • the diisocyanate compound may be, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate or 4,4'-methylenediphenyl diisocyanate.
  • the hydroxy-terminated siloxane of the above chemical formula 1 may be a reaction product of a hydroxy-terminated siloxane of the above chemical formula 1a and a phosphor-containing compound (an aromatic or an aliphatic phosphate compound).
  • the phosphor-containing compound may have a structure of the following chemical formula 1b.
  • R 4 is the same as defined in chemical formula 3 above, and Z independently represents phosphorus, halogen atom, hydroxyl group, carboxyl group, alkyl group (having 1 to 20 carbon atoms), alkoxy group or aryl group.
  • the polysiloxane-polycarbonate copolymer comprises, as repeating units, a hydroxy-terminated siloxane of the above chemical formula 1a or chemical formula 1; and a polycarbonate block of the following chemical formula 4:
  • R 5 represents aromatic hydrocarbon group having 6 to 30 carbon atoms that is unsubstituted or substituted with alkyl group having 1 to 20 carbon atoms (for example, alkyl group having 1 to 13 carbon atoms), cycloalkyl group (for example, cycloalkyl group having 3 to 6 carbon atoms), alkenyl group (for example, alkenyl group having 2 to 13 carbon atoms), alkoxy group (for example, alkoxy group having 1 to 13 carbon atoms), halogen atom or nitro.
  • alkyl group having 1 to 20 carbon atoms for example, alkyl group having 1 to 13 carbon atoms
  • cycloalkyl group for example, cycloalkyl group having 3 to 6 carbon atoms
  • alkenyl group for example, alkenyl group having 2 to 13 carbon atoms
  • alkoxy group for example, alkoxy group having 1 to 13 carbon atoms
  • halogen atom or nitro for example, alkyl group having
  • the aromatic hydrocarbon group may be derived from a compound of the following chemical formula 4a.
  • X represents alkylene group; linear, branched or cyclic alkylene group having no functional group; or linear, branched or cyclic alkylene group comprising a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, isobutylphenyl, etc.
  • X may be linear or branched alkylene group having 1 to 10 carbon atoms, or cyclic alkylene group having 3 to 6 carbon atoms.
  • R 6 independently represents hydrogen atom, halogen atom or alkyl group ⁇ for example, linear or branched alkyl group having 1 to 20 carbon atoms, or cyclic alkyl group having 3 to 20 (preferably, 3 to 6) carbon atoms.
  • n and m independently represent an integer of 0 to 4.
  • the compound of the above chemical 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-hydroxyphenyl)ethane, 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,
  • the representative one is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • US Patent Nos. 2,999,835; 3,028,365; 3,153,008 and 3,334,154 may be referred to.
  • the above dihydric phenol may be used alone or in combination of two or more of them.
  • carbonate precursor for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenylcarbonate, dimethylcarbonate, etc. may be used as another monomer of the polycarbonate resin, but it is not limited thereto.
  • the amount of siloxane in the polysiloxane-polycarbonate copolymer is 10 to 35% by weight, preferably 15 to 30% by weight, and more preferably 20 to 30% by weight. If the amount of siloxane is less than 10% by weight based on total weight of the copolymer, the effect of improving low-temperature impact resistance may be insufficient as compared with the requirement of the present invention. If the amount of siloxane is greater than 35% by weight, the relative amount of polycarbonate in the copolymer decreases and thus physical properties such as flowability, heat resistance, impact resistance at room temperature, transparency, etc. may be deteriorated.
  • the polysiloxane-polycarbonate copolymer may have a viscosity average molecular weight (M v ) of from 10,000 to 70,000, and more preferably from 15,000 to 30,000. If the viscosity average molecular weight of the copolymer is less than 10,000, its mechanical properties may be deteriorated severely. If the viscosity average molecular weight is greater than 70,000, the melt viscosity increases and thus there may be a problem in resin processing.
  • M v viscosity average molecular weight
  • PC Polycarbonate
  • polycarbonate which is comprised in the polycarbonate resin composition of the present invention together with the polysiloxane-polycarbonate copolymer. Any conventional polycarbonate resin may be used.
  • the polycarbonate has a viscosity average molecular weight of from 10,000 to 50,000, and more preferably 15,000 to 35,000. If the viscosity average molecular weight of the polycarbonate is less than 10,000, its mechanical properties may be deteriorated severely. If the viscosity average molecular weight is greater than 50,000, the flowability decreases and thus there may be a problem in resin processing.
  • the weight ratio of polysiloxane-polycarbonate copolymer : polycarbonate in the polycarbonate resin composition of the present invention is preferably 10 : 90 to 50 : 50, and more preferably 15 : 85 to 40 : 60. If the weight ratio of the copolymer to the polycarbonate is less than 10 : 90, the effect of improving low-temperature impact resistance may be insufficient as compared with the requirement of the present invention. If the weight ratio is greater than 50 : 50, physical properties such as flowability, heat resistance, impact resistance at room temperature, transparency, etc. may be deteriorated.
  • the amount of siloxane in the present polycarbonate resin composition comprising a polysiloxane-polycarbonate copolymer and a polycarbonate together is preferably from 3 to 12% by weight, and more preferably from 4 to 10% by weight.
  • the amount of siloxane in the total composition is within a range of from 3 to 12% by weight, the low-temperature impact resistance can be improved significantly (more than two-fold) while securing good flowability and impact resistance at room temperature.
  • the polycarbonate resin composition of the present invention may be prepared through the steps of: reacting hydroxy-terminated siloxane and oligomeric polycarbonate under an interfacial reaction condition consisting of an aqueous alkaline solution and an organic phase to form a polysiloxane-polycarbonate intermediate; polymerizing the intermediate by using a first polymerization catalyst to prepare a polysiloxane-polycarbonate copolymer; and mixing the prepared polysiloxane-polycarbonate copolymer and a polycarbonate.
  • the step for forming the intermediate may comprise a step of 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). If the mixing ratio of hydroxy-terminated siloxane is less than 10, the effect of improving low-temperature impact resistance may be insufficient as compared with the requirement of the present invention. If the mixing ratio of hydroxy-terminated siloxane is greater than 35, the relative amount of polycarbonate in the copolymer decreases and thus physical properties such as flowability, heat resistance, impact resistance at room temperature, transparency, etc. may be deteriorated.
  • the polycarbonate used in the preparation of the polysiloxane-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 viscosity average molecular weight of the oligomeric polycarbonate is less than 800, the molecular weight distribution may broaden and physical properties may be deteriorated. If the viscosity average molecular weight of the oligomeric polycarbonate is greater than 20,000, the reactivity may be lowered.
  • the oligomeric polycarbonate may be prepared by adding the above-explained dihydric phenol compound in an aqueous alkaline solution to make it in a phenol salt state, and then adding the phenol compound in a phenol salt state to dichloromethane containing injected phosgene gas for reaction.
  • To prepare the oligomer it is preferable to maintain the molar ratio of phosgene to bisphenol within a range of about 1 : 1 to 1.5 : 1, and more preferably 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 greater than 1.5, the molecular weight increases excessively and thus the processability may be lowered.
  • the above reaction of forming an oligomer may generally be conducted at a temperature range of about 15 to 60°C.
  • alkali metal hydroxide for example, sodium hydroxide
  • alkali metal hydroxide for example, sodium hydroxide
  • the step for forming the intermediate comprises a step of forming a mixture comprising the hydroxy-terminated siloxane and the oligomeric polycarbonate, wherein the mixture may further comprise a phase transfer catalyst, a molecular weight-controlling agent and a second polymerization catalyst.
  • the step for forming the intermediate may comprise a step of forming a mixture comprising the hydroxy-terminated siloxane and the oligomeric polycarbonate; and after the reaction of the hydroxy-terminated siloxane and the oligomeric polycarbonate is completed, a step of extracting an organic phase from the resulting mixture, wherein the step of polymerizing the intermediate may comprise a step of providing the first polymerization catalyst to the extracted organic phase.
  • the polysiloxane-polycarbonate copolymer may be prepared by adding the hydroxy-terminated siloxane of the above chemical formula 1a or chemical formula 1 to a mixture of organic phase/aqueous phase containing the polycarbonate, and subsequently feeding a molecular weight-controlling agent and a catalyst.
  • a monofunctional compound similar to a monomer used in preparation of polycarbonate may be used.
  • the monofunctional compound may be, for example, a derivative based on phenol such as p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononylphenol, or an aliphatic alcohol.
  • PTBP p-tert-butylphenol
  • PTBP p-tert-butylphenol
  • 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 of the following chemical formula 5.
  • R 7 represents alkyl group having 1 to 10 carbon atoms
  • Q represents nitrogen or phosphorus
  • X represents halogen atom or -OR 8 wherein R 8 represents hydrogen atom, alkyl group having 1 to 18 carbon atoms or aryl group having 6 to 18 carbon atoms.
  • 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 where R 8 represents hydrogen atom, alkyl group having 1 to 18 carbon atoms or aryl group having 6 to 18 carbon atoms.
  • the amount of the phase transfer catalyst is preferably about 0.01 to 10% by weight, and more preferably 0.1 to 10% by weight based on total weight of the hydroxy-terminated siloxane and the oligomeric polycarbonate. If the amount of the phase transfer catalyst is less than 0.01% by weight, the reactivity may be lowered. If the amount of the phase transfer catalyst is greater than 10% by weight, precipitation may happen or the transparency may be deteriorated.
  • the organic phase dispersed in methylene chloride is washed with alkali and then separated. Subsequently, the organic phase is washed with 0.1 N solution of hydrochloric acid and then rinsed with distilled water 2 or 3 times. After rinsing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted constantly and granulation is conducted 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 low and thus the granulation time may be too long.
  • the temperature of the pure water is higher than 100°C, it may be difficult to obtain the polycarbonate in uniformly sized morphology.
  • the method of mixing the polysiloxane-polycarbonate copolymer and the polycarbonate prepared as such is not especially limited.
  • the polysiloxane-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.
  • An interfacial reaction of bisphenol A in an aqueous solution phase and phosgene gas was conducted in the presence of methylene chloride to prepare 400mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000.
  • oligomeric polycarbonate mixture 20% by weight of the hydroxy-terminated siloxane having urethane linkage of chemical formula 6 dissolved in methylene chloride, 1.8mL of tetrabutylammonium chloride (TBACl), 1.5g of p- tert -butylphenol (PTBP) and 275 ⁇ l of triethylamine (TEA, 15 wt% solution) were admixed and reacted for 30 minutes.
  • TBACl tetrabutylammonium chloride
  • PTBP p- tert -butylphenol
  • TEA triethylamine
  • the reacted oligomeric polycarbonate mixture was kept for phase separation. After the phases were separated, only the organic phase was collected and thereto 170g of an aqueous solution of sodium hydroxide, 370g of methylene chloride and 300 ⁇ l of triethylamine (15 wt% solution) were admixed and reacted for 2 hours. After phase separation, the viscosity-increased organic phase was washed with alkali and separated. Next, the resulting organic phase was washed with 0.1N hydrochloric acid solution and then rinsed with distilled water 2 to 3 times. After rinsing was completed, the concentration of the organic phase was adjusted constantly and then granulation was conducted by using a constant amount of pure water at 76°C.
  • the product was dried first at 110°C for 8 hours, and second at 120°C for 10 hours.
  • the synthesis was confirmed by H-NMR analysis wherein the peak of methylene group of the polysiloxane was observed at 2.65ppm, the peak of methoxy group was observed at 3.85ppm, and the peak of hydrogen of benzene ring was observed at 7.1 to 7.5ppm.
  • a polycarbonate resin composition was prepared by mixing the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) in a weight ratio of 40 : 60.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • oligomeric polycarbonate mixture 30% by weight of the hydroxy-terminated siloxane having ester linkage of chemical formula 7 dissolved in methylene chloride, 1.8mL of tetrabutylammonium chloride (TBACl), 1.5g of p- tert -butylphenol (PTBP) and 275 ⁇ l of triethylamine (TEA, 15 wt% aqueous solution) were admixed and reacted for 30 minutes. The reacted oligomeric polycarbonate mixture was kept for phase separation.
  • TBACl tetrabutylammonium chloride
  • PTBP p- tert -butylphenol
  • TEA triethylamine
  • the product was dried first at 110°C for 8 hours, and second at 120°C for 10 hours.
  • the synthesis of the copolymer was confirmed by H-NMR analysis wherein the peaks of methylene group of the polysiloxane were observed at 2.6ppm and 2.65ppm, the peak of hydrogen of benzene ring of TCL was observed at 8.35ppm, and the peak of hydrogen of benzene ring of the polysiloxane was observed at 6.95 to 7.5ppm.
  • a polycarbonate resin composition was prepared by mixing the prepared polysiloxane-polycarbonate copolymer and polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) in a weight ratio of 20 : 80.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 20% by weight of hydroxy-terminated siloxane of the above chemical formula 7, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3027PJ, M v : 24,600, Samyang Corporation) were mixed in a weight ratio of 30 : 70.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 20% by weight of hydroxy-terminated siloxane of the following chemical formula 8, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) were mixed in a weight ratio of 30 : 70.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 30% by weight of hydroxy-terminated siloxane of the above chemical formula 8, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) were mixed in a weight ratio of 15 : 85.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 8% by weight of hydroxy-terminated siloxane of the above chemical formula 7, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) were mixed in a weight ratio of 60 : 40.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 9% by weight of hydroxy-terminated siloxane of the above chemical formula 8, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3027PJ, M v : 24,600, Samyang Corporation) were mixed in a weight ratio of 30 : 70. The properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 45% by weight of hydroxy-terminated siloxane of the above chemical formula 8, and the prepared polysiloxane-polycarbonate copolymer and a polycarbonate (3027PJ, M v : 24,600, Samyang Corporation) were mixed in a weight ratio of 40 : 60.
  • the 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 thus its low-temperature impact resistance could not be measured.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 8% by weight of hydroxy-terminated siloxane of the above chemical formula 7, and the prepared polysiloxane-polycarbonate copolymer was used alone without mixing it with a polycarbonate.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that the polysiloxane-polycarbonate copolymer was prepared by using 20% by weight of hydroxy-terminated siloxane of the above chemical formula 7, and the prepared polysiloxane-polycarbonate copolymer was used alone without mixing it with a polycarbonate.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that a polycarbonate (3022PJ, M v : 21,000, Samyang Corporation) was used alone without any polysiloxane-polycarbonate copolymer.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • a polycarbonate resin composition was prepared by the same method as described in Example 1, except that a polycarbonate (3030PJ, M v : 31,200, Samyang Corporation) was used alone without any polysiloxane-polycarbonate copolymer.
  • the properties of the prepared polycarbonate resin composition were measured, and the results are shown in Table 1 below.
  • the polycarbonate resin compositions prepared according to the Examples showed better impact resistance at room temperature and flowability, and remarkably superior low-temperature impact resistance, as compared with the polycarbonate resin compositions prepared according to the Comparative Examples.
  • Viscosity average molecular weight (M v ) The viscosity of methylene chloride solution was measured by using an Ubbelohde Viscometer at 20°C, and the limiting viscosity [ ⁇ ] therefrom was calculated according to the following equation.
  • Impact resistance was measured by using an impact test machine (RESIL IMPACTOR, CEAST Co., Ltd.) at room temperature and -50°C.
  • melt index The melt index, which indicates flowability under certain temperatures and loads, was measured at 300°C under a load of 1.2kg f according to ASTM D1238.

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Abstract

La présente invention concerne une composition de résine de polycarbonate et un procédé de fabrication de cette composition. Plus spécifiquement, la présente invention concerne une composition de résine de polycarbonate qui comprend un copolymère polysiloxane-polycarbonate ayant une teneur élevée en siloxane et un polycarbonate dans un rapport de mélange approprié, et a ainsi une résistance au choc améliorée à basse température, une aptitude à l'écoulement améliorée et une résistance améliorée à la chaleur ; et un procédé de fabrication de celle-ci.
PCT/KR2012/008834 2011-10-31 2012-10-26 Composition de résine de polycarbonate ayant une résistance au choc améliorée à basse température et son procédé de fabrication WO2013066000A1 (fr)

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JP2016524646A (ja) * 2013-06-17 2016-08-18 サムヤン コーポレイションＳａｍｙａｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 難燃性と透明性に優れた熱可塑性共重合体樹脂及びその製造方法
JP2017501245A (ja) * 2014-12-04 2017-01-12 エルジー・ケム・リミテッド コポリカーボネートおよびこれを含む組成物
EP3067379A4 (fr) * 2014-12-04 2017-09-06 LG Chem, Ltd. Copolycarbonate et composition le contenant
JP2018530663A (ja) * 2015-10-15 2018-10-18 サムヤン コーポレイション 透明性及び難燃性が向上されたポリシロキサン−ポリカーボネート共重合体及びその製造方法
CN115785642A (zh) * 2022-12-14 2023-03-14 无锡赢同新材料科技有限公司 一种耐低温高模量电磁屏蔽材料及其制备方法

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EP3004207A2 (fr) * 2013-05-31 2016-04-13 Momentive Performance Materials Japan LLC Polysiloxanes fonctionnels contenant un groupe phényle et compositions de copolymères polycarbonate-polysiloxane fabriquées à partir de ceux-ci
WO2015002427A1 (fr) 2013-07-01 2015-01-08 (주) 엘지화학 Composé de polyorganosiloxane, son procédé de préparation, et résine copolycarbonate le comprenant
KR101675197B1 (ko) * 2013-07-01 2016-11-10 주식회사 엘지화학 폴리오르가노실록산 및 코폴리카보네이트 수지
KR101530322B1 (ko) * 2013-07-24 2015-06-22 주식회사 삼양사 투명성이 향상된 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
KR101528362B1 (ko) * 2013-07-25 2015-06-19 주식회사 삼양사 투명성이 향상된 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
KR101579618B1 (ko) * 2013-09-17 2015-12-22 주식회사 엘지화학 코폴리카보네이트 수지 및 이를 포함하는 물품
KR101666412B1 (ko) * 2013-12-05 2016-10-17 주식회사 삼양사 장시간 성형 가공시 열안정성이 뛰어나고, 내화학성 및 저온 충격 강도가 개선된 고유동성 폴리카보네이트 수지 조성물 및 그 제조방법
KR101837613B1 (ko) * 2014-05-21 2018-03-13 주식회사 삼양사 투명성 및 내충격성이 향상된 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
WO2016036203A1 (fr) * 2014-09-05 2016-03-10 주식회사 엘지화학 Copolycarbonate et composition le contenant
KR101779188B1 (ko) 2014-09-05 2017-09-15 주식회사 엘지화학 코폴리카보네이트 및 이를 포함하는 조성물
KR101768277B1 (ko) * 2014-09-05 2017-08-16 삼성에스디아이 주식회사 프라이머 조성물 및 이를 이용한 플라스틱 글레이징
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KR101924199B1 (ko) 2016-02-01 2018-11-30 주식회사 엘지화학 신규한 폴리오르가노실록산 및 이를 사용하여 제조되는 코폴리카보네이트
KR102383997B1 (ko) * 2020-04-24 2022-04-08 주식회사 삼양사 히드록시 말단 폴리실록산 혼합물을 이용한 폴리실록산-폴리카보네이트 공중합체 및 그 제조방법
KR102733236B1 (ko) * 2021-12-24 2024-11-25 주식회사 삼양사 폴리실록산-폴리카보네이트 공중합체 및 그 제조 방법

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WO2014191973A1 (fr) * 2013-05-31 2014-12-04 Sabic Innovative Plastics Ip B.V. Compositions à base d'un copolymère de polycarbonate-siloxane présentant un aspect amélioré
JP2016524646A (ja) * 2013-06-17 2016-08-18 サムヤン コーポレイションＳａｍｙａｎｇ Ｃｏｒｐｏｒａｔｉｏｎ 難燃性と透明性に優れた熱可塑性共重合体樹脂及びその製造方法
US9951187B2 (en) 2013-06-17 2018-04-24 Samyang Corporation Thermoplastic copolymer resin having excellent flame retardancy and transparency and preparation method therefor
EP3067379A4 (fr) * 2014-12-04 2017-09-06 LG Chem, Ltd. Copolycarbonate et composition le contenant
JP2017501251A (ja) * 2014-12-04 2017-01-12 エルジー・ケム・リミテッド コポリカーボネートおよびこれを含む組成物
JP2017501246A (ja) * 2014-12-04 2017-01-12 エルジー・ケム・リミテッド コポリカーボネートおよびこれを含む組成物
EP3064523A4 (fr) * 2014-12-04 2017-09-13 LG Chem, Ltd. Copolycarbonate et composition le comprenant
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US10696796B2 (en) 2015-10-15 2020-06-30 Samyang Corporation Polysiloxane-polycarbonate copolymer with improved transparency and flame retardancy and method for producing same
CN115785642A (zh) * 2022-12-14 2023-03-14 无锡赢同新材料科技有限公司 一种耐低温高模量电磁屏蔽材料及其制备方法
CN115785642B (zh) * 2022-12-14 2024-05-14 无锡赢同新材料科技有限公司 一种耐低温高模量电磁屏蔽材料及其制备方法

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