WO2016188478A1 - 一种聚碳酸酯组合物及其制备方法 - Google Patents

一种聚碳酸酯组合物及其制备方法 Download PDF

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WO2016188478A1
WO2016188478A1 PCT/CN2016/083633 CN2016083633W WO2016188478A1 WO 2016188478 A1 WO2016188478 A1 WO 2016188478A1 CN 2016083633 W CN2016083633 W CN 2016083633W WO 2016188478 A1 WO2016188478 A1 WO 2016188478A1
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parts
group
formula
polycarbonate
flame retardant
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PCT/CN2016/083633
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English (en)
French (fr)
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谢修好
孙东海
岑茵
佟伟
艾军伟
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金发科技股份有限公司
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Priority to EP16799365.8A priority Critical patent/EP3305849B1/en
Priority to US15/576,853 priority patent/US10696841B2/en
Publication of WO2016188478A1 publication Critical patent/WO2016188478A1/zh

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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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
  • PC Polycarbonate
  • EP-A900827 improves the solvent resistance of the polycarbonate alloy by improving the ABS of the emulsion method, and although the solvent resistance of the polycarbonate alloy is improved, the defect is that the thermal stability of the system is lacking;
  • WO- A2007/065579 describes the use of organic carboxylic acids to stabilize the solvent resistance of polycarbonates, but deficiencies can cause degradation of the polycarbonate and even lead to molding defects.
  • the inventors have surprisingly found through extensive experiments that when a specific content of a phenolic substance and a hindered phenolic substance are added to a polycarbonate composition formulation, the obtained polycarbonate composition has excellent solvent resistance and fluidity. And can maintain good thermal stability.
  • Another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.
  • a polycarbonate composition comprising, by weight, the following composition:
  • the sum of the weight components of the six components a, b, c, d, e, and f is 100 parts;
  • R 1 and R 5 represent a hydrogen group other than a hindered group, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or a carbonyl group, and an ester group
  • R 2 , R 3 and R 4 represent a substituent having a hydrogen atom, preferably hydrogen. atom;
  • formula of formula II is C n O m R, wherein n is greater than 2, m is greater than 2, and R represents a hetero atom, preferably a long chain substituent of an N atom and an S atom, more preferably an aromatic group containing a symmetric structure. N long chain substituents.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the six components a, b, c, d, e, and f is 100 parts.
  • R 1 and R 5 represent a hydrogen group other than a hindered group, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or a carbonyl group, and an ester group
  • R 2 , R 3 and R 4 represent a substituent having a hydrogen atom, preferably hydrogen. atom;
  • formula of formula II is C n O m R, wherein n is greater than 2, m is greater than 2, and R represents a hetero atom, preferably a long chain substituent of an N atom and an S atom, more preferably an aromatic group containing a symmetric structure. N long chain substituents.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the six components a, b, c, d, e, and f is 100 parts.
  • R 1 and R 5 represent a hydrogen group other than a hindered group, an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group or a carbonyl group, and an ester group
  • R 2 , R 3 and R 4 represent a substituent having a hydrogen atom, preferably hydrogen. atom;
  • formula of formula II is C n O m R, wherein n is greater than 2, m is greater than 2, and R represents a hetero atom, preferably a long chain substituent of an N atom and an S atom, more preferably an aromatic group containing a symmetric structure. N long chain substituents.
  • the test method for the content of the phenolic substance after weighing 2 g of the polycarbonate composition with an electronic balance, the sample is placed in a constant temperature oven at a preset temperature of 120 ° C and the temperature is uniformly stabilized, and then placed in Soxhlet.
  • the extraction device was subjected to methanol extraction, the extraction temperature was 85 ° C, and the time was 48 h.
  • the extract is injected into the adsorption column of C18 for separation and quantification.
  • the specific outflow time of the standard and the extrapolation method can be calculated.
  • the content of phenolic substances is obtained.
  • the phenolic material of formula I is selected from one or more of the group consisting of phenol, p-chlorophenol, 2,4,6-tribromophenol, and long chain alkyl phenols.
  • the hindered phenolic material of formula II is selected from the group consisting of 3,5-di-tert-butylphenol, preferably 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid octadecyl alcohol ester.
  • the hindered phenolic substance as described in Formula II may have different weight percentages, and the phenolic substance as described in Formula I in the polycarbonate composition
  • the weight percentage of the hindered phenolic substance as described in formula II is from 0.001 to 20.
  • the polycarbonate is selected from one or more of an aromatic polycarbonate, an aliphatic polycarbonate, an aromatic-aliphatic polycarbonate, a branched polycarbonate, and a siloxane copolycarbonate; preferably An aromatic polycarbonate which is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, preferably a viscosity average An aromatic polycarbonate having a molecular weight of 16,000 to 28,000.
  • the rubber-modified graft polymer is selected from one or more of a graft copolymer prepared by a bulk polymerization method, an emulsion polymerization method, or a bulk-suspension polymerization method.
  • Bulk polymerization including sol, prepolymerization, polymerization, devolatilization and granulation. Dissolving the rubber in ethylbenzene and styrene, adding the monomer to the raw material liquid according to the formula amount, and inputting the prepared raw material liquid into the pre-polycarbonate for pre-polymerization. During the polymerization process, the rubber grafting monomer is simultaneously The bulk copolymer is separated from the solution to form a discontinuous phase dispersed in the continuous phase of the raw material liquid. When there is enough monomer to polymerize, the discontinuous phase of the copolymer becomes a continuous phase, and the grafted rubber is not formed. The continuous phase is dispersed in a continuous copolymer phase to complete the phase transition, and finally subjected to further polymerization, vacuum degassing, extrusion, cooling and pelletizing to obtain a final product;
  • Bulk-suspension polymerization method adjust the rubber and monomer solution according to the formula, and simultaneously add a polymerization regulator and a radical initiator, and carry out bulk polymerization of the monomer mixture at 80 ° C - 120 ° C, stirring constantly during the polymerization, and going Ionic water and a suspending agent are added to the mixture to disperse the mixture, and then suspension polymerization is carried out by using a radical catalyst to obtain a certain degree of polymerization, followed by agglomeration, filtration, washing, dehydration and drying, followed by granulation to obtain a product.
  • Emulsion polymerization method the rubber is grafted by adding the monomer mixture to the rubber latex at a polymerization temperature of 50 ° C to 80 ° C in an initiator, deionized water, an emulsifier and a crosslinking agent, and finally washing, dehydrating and drying. After granulation, the product is obtained.
  • the rubber-modified graft polymer is selected from the group consisting of the following graft polymers comprising b.1 on b.2:
  • B.1.1 50 parts - 95 parts of styrene, styrene derivatives such as ⁇ -methylstyrene, p-benzyl styrene, divinyl styrene, C1-C8-alkyl methacrylate, acrylic acid One or more of a C1-C8-alkyl ester, a dimethylsiloxane, a phenylsiloxane, a polyalkylsiloxane;
  • a Tg rubber polymer substrate having a thickness of less than 10 ° C, less than 0 ° C, less than -10 ° C or between -40 ° C and -80 ° C, and a rigid polymer grafted to a rubber polymer substrate are suitable for use.
  • the rubber material includes, for example, a conjugated diene, a rigid polymer such as styrene, acrylonitrile, acrylate, etc., an olefin rubber such as an ethylene propylene copolymer EPR or an ethylene propylene diene monomer rubber EPDM, an ethylene-vinyl acetate rubber; Silicone rubber; an elastomeric C1-8 alkyl methacrylate, an elastomeric copolymer of a C1-8 alkyl methacrylate with butadiene or styrene; or a combination comprising at least one of the foregoing elastomers.
  • a conjugated diene a rigid polymer such as styrene, acrylonitrile, acrylate, etc.
  • an olefin rubber such as an ethylene propylene copolymer EPR or an ethylene propylene diene monomer rubber EPDM, an ethylene-vinyl acetate rubber
  • Materials suitable for the rigid phase include, for example, monovinyl aromatic monomers such as styrene and a-methylstyrene and monovinyl monomers such as acrylonitrile, acrylic acid, methacrylic acid, and C1-C6 of acrylic acid and methacrylic acid.
  • the ester is specifically methyl methacrylate.
  • the rubber modified graft polymer is selected from the group consisting of styrene-butadiene-styrene SBS, styrene-butadiene rubber SBR, styrene-ethylene-butadiene-styrene SEBS, acrylonitrile - Butadiene-styrene graft copolymer ABS, acrylonitrile-styrene-acrylic acid terpolymer ASA or methyl methacrylate-butadiene-styrene graft copolymer MBS, and styrene-acrylonitrile
  • the SAN formation preferably an acrylonitrile-butadiene-styrene graft copolymer ABS; wherein the particle size of the MBS is preferably 0.1 um to 0.5 um, and the bulk polymerization method ABS particle size is preferably 0.1 um - 2um, the emulsion polymerization ABS particle size is
  • the flame retardant is selected from the group consisting of a halogen-based flame retardant or a halogen-free flame retardant, preferably a halogen-free flame retardant;
  • the halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyphenylene ether, and brominated double Phenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, all One or more of bromotricyclopentadecane or brominated aromatic crosslinked polymer, preferably brominated polystyrene;
  • the halogen-free flame retardant is selected from the group consisting of nitrogen-containing flame retardants and phosphorus-containing flame retardants Or one or more of the nitrogen and phosphorus containing flame retardants, preferably a
  • the phosphorus-containing flame retardant is selected from the group consisting of triphenyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, trimethylphenyl phosphate, and tris(2,4,6-trimethyl phosphate).
  • Phenyl) ester tris(2,4-di-tert-butylphenyl) phosphate, tris(2,6-di-tert-butylphenyl) phosphate, resorcinol bis(diphenyl phosphate) , hydroquinone bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate), p-phenylene One or more of phenol bis(2,6-dimethylphenyl phosphate).
  • the synergistic flame retardant is selected from the group consisting of silicon-containing substances and/or fluorine-containing substances;
  • the silicon-containing substance is selected from one or more of silicone oil, silicone, and siloxane copolymer;
  • the fluorine species is selected from the group consisting of polytetrafluoroethylene and/or masterbatches containing polytetrafluoroethylene.
  • a siloxane copolymer means a polydimethylsiloxane block in which a polydimethylsiloxane block has a degree of polymerization of 30 to 100 dimethylsiloxane moieties, and the repeating unit may have a specific The block length and enables the composition to have relatively good toughness at low temperatures.
  • the above polycarbonate composition further includes other processing aids selected from one or more of a stabilizer, a plasticizer, a mold release agent, a filler, and a colorant.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphonic acid Ester, trimethyl phosphate, etc., organic phosphite, alkylated monohydric or polyhydric phenol, alkylation reaction product of polyhydric phenol and diene, butylated reaction product of p-cresol or dicyclopentadiene , alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones Or a variety of combinations.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl
  • a suitable plasticizer is a phthalate.
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable fillers include glass fiber, glass powder, wollastonite, calcium carbonate, barium sulfate, talc, metal powder, and the like.
  • Suitable colorants include various pigments, dyes such as metal oxides of inorganic pigments and zinc oxides of mixed metal oxides, titanium oxide, iron oxides, sulfides such as zinc sulfide, etc.; aluminates, silicates, chromates , ferrite, etc., carbon black, ultramarine; organic pigments such as azo, diazo, anthraquinone, anthrone, phthalocyanine, quinoline, naphthalene, ketone, azine and the like.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the polycarbonate composition of the present invention can be used in outdoor and indoor applications, such as housing parts of various types and sizes, household appliances such as televisions, printers, modem housings, display housings, etc., or automotive parts for outdoor use,
  • housing parts of various types and sizes household appliances such as televisions, printers, modem housings, display housings, etc., or automotive parts for outdoor use,
  • the invention has the following beneficial effects:
  • the present invention provides a polycarbonate composition having excellent solvent resistance when a specific content of the phenolic substance as described in Formula I and a hindered phenolic substance as described in Formula II are added to the polycarbonate composition formulation. And fluidity, and can maintain good thermal stability.
  • Test method for alcohol resistance (%) The test piece was prepared by using an 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd. under the conditions of a cylinder temperature of 280 ° C and a mold temperature of 80 ° C.
  • the JIS No. 1 dumbbell type test piece prepared by the above method was immersed in methanol at 23 ° C for 7 days.
  • the tensile yield strength before and after the test piece immersion treatment was measured in accordance with the method of JIS K7113.
  • the ratio (%) of "the tensile yield strength of the test piece after the immersion treatment" to the "tensile yield strength of the test piece before the immersion treatment” was determined as the alcohol resistance (%).
  • Test method for processing defects A molded article having a size of 10 cm (length) ⁇ 4 cm (width) ⁇ 1 mm (thickness) was obtained by injection molding, and its appearance (hue, surface condition) was observed. Molded articles that are not unpleasant in hue and have a smooth and good surface condition can be evaluated as "good”; those that are unsightly or have a rough and poor surface condition can be considered “poor”.
  • Flow length (mm) test method injection molding of molten resin in a flat-plate mold having a thickness of 0.5 mm and a width of 40 mm at a cylinder temperature of 280 ° C, an injection pressure of 74 MPa, and a mold temperature of 80 ° C.
  • the flow length is measured as the flow length.
  • the maximum flow length is The sum of the minimum flow length sum divided by 2 is taken as the flow length. The higher the fluidity, the higher the value of the material.
  • Test method of thermal decomposition temperature 10 mg of the composition was heated from 30° C. to 500° C. at 20° C./min under a nitrogen atmosphere using a thermogravimetric measuring apparatus ("TGA-7" manufactured by PerkinElmer Co., Ltd.). The temperature which is reduced by 5 wt% with respect to the mass before the temperature rise is taken as the thermal decomposition temperature, and the better the thermal decomposition stability, the better the thermal stability.
  • TGA-7 thermogravimetric measuring apparatus
  • Component a-1 FN1900 (Japan Light)
  • Component a-2 H2200 (Mitsubishi, Japan)
  • Component b phenol (Shanghai TCI);
  • a hindered phenolic substance as described in Formula II for use in the present invention is:
  • Component c octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate 1076 (BASF);
  • Rubber modified graft polymer used in the present invention Rubber modified graft polymer used in the present invention:
  • Component d-1 ABS 8391 (Shanghai Gaoqiao)
  • Component d-2 MBS EM500 (LG, Korea)
  • the synergistic flame retardant used in the present invention is a synergistic flame retardant used in the present invention.
  • Component f PTFE (polytetrafluoroethylene) as a synergistic flame retardant.
  • the phenolic substance as described in Formula I, the hindered phenolic substance as described in Formula II, and the polycarbonate are uniformly mixed in a high-mixer to obtain a mixed material; the mixed material is modified with rubber.
  • Graft polymer, flame retardant, synergistic flame retardant are added to the twin-screw extruder through the main feed port, extruded, cooled by water, granulated to obtain columnar particles of polycarbonate composition;
  • the alcohol resistance (%), processing defects, flow length and thermal decomposition temperature performance of the composition are shown in Table 1.
  • the present invention selects a specific amount of the phenolic substance as described in Formula I and the hindered phenolic substance as described in Formula II in the polycarbonate composition formulation.
  • the obtained polycarbonate composition has excellent solvent resistance and fluidity, and can maintain good thermal stability.

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Abstract

公开了一种聚碳酸酯组合物，它包括以下组成(wt)： a、30份‐86份的聚碳酸酯； b、0.0001‐1份如式I所述的苯酚类物质； c、0.01‐5份的位阻酚物质； d、8份‐50份的橡胶改性的接枝聚合物； e、5份‐25份的阻燃剂； f、0‐10份的阻燃协效剂；其中，a、b、c、d、e、f六种组分的重量份之和为100份；其中式I的结构式：其中R 1和R 5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R 2，R 3，R 4代表取代基，优选氢原子。所述聚碳酸酯组合物具有优异的耐溶剂性能和流动性，并能保持良好的热稳定性。

Description

一种聚碳酸酯组合物及其制备方法 技术领域
本发明涉及工程塑料技术领域，特别涉及一种聚碳酸酯组合物及其制备方法。
背景技术
聚碳酸酯(PC)是耐冲击性，耐热性，热稳定性优异的热塑性树脂，广泛应用与电子电器，信息技术设备，机械，汽车等领域，为改善其加工性能及对缺口冲击敏感的缺点，通常可加入橡胶类改性聚合物，如ABS、MBS等，特别是以PC和ABS为主要原料的PC/ABS合金是一种重要的工程塑料，可综合两者的优良性能，做到物理性能以及加工性能得到提高，但是PC/ABS合金的耐溶剂性能较差是因为PC树脂为非结晶材料，会因为溶剂深入使材料制品上产生裂纹等不良状况，严重的会导致使用性能失效，因此迫切需要一种耐溶剂性优异的PC/ABS合金。
现有技术中，如EP-A900827通过改进乳液法的ABS来提高聚碳酸酯合金的耐溶剂性能，虽然提高了聚碳酸酯合金的耐溶剂性能，但缺陷是体系的热稳定性欠缺；WO-A2007/065579描述了使用有机羧酸类来稳定聚碳酸酯的耐溶剂性能，但不足之处会引起聚碳酸酯的降解甚至导致成型缺陷。
到目前为止，关于引入苯酚类物质以及位阻酚物质对所述聚碳酸酯组合物的耐溶剂性能、流动性和热稳定性的影响还未见报道。
本发明人经过大量实验惊讶地发现，选用在聚碳酸酯组合物配方中添加特定含量的苯酚类物质以及位阻酚物质时，得到的聚碳酸酯组合物具有优异的耐溶剂性能和流动性，并能保持良好的热稳定性。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一种具有优异的耐溶剂性能和流动性，并能保持良好的热稳定性的聚碳酸酯组合物。
本发明的另一目的是提供上述聚碳酸酯组合物的制备方法。
本发明是通过以下技术方案实现的：
一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-86份的聚碳酸酯；
b、0.0001份-1份如式I所述的苯酚类物质；
c、0.01-5份如式II所述的位阻酚物质；
d、8份-50份的橡胶改性的接枝聚合物；
e、5份-25份的阻燃剂；
f、0-10份的阻燃协效剂；
其中，a、b、c、d、e、f六种组分的重量份之和为100份；
其中式I的结构式：
Figure PCTCN2016083633-appb-000001
其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-86份的聚碳酸酯；
b、0.005份-0.2份如式I所述的苯酚类物质；
c、0.03-1份如式II所述的位阻酚物质；
d、8份-50份的橡胶改性的接枝聚合物；
e、5份-25份的阻燃剂；
f、0-10份的阻燃协效剂；
其中，a、b、c、d、e、f六种组分的重量份之和为100份，
其中式I的结构式：
Figure PCTCN2016083633-appb-000002
其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
更优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、30份-86份的聚碳酸酯；
b、0.01份-0.05份如式I所述的苯酚类物质；
c、0.05-0.1份如式II所述的位阻酚物质；
d、8份-50份的橡胶改性的接枝聚合物；
e、5份-25份的阻燃剂；
f、0-10份的阻燃协效剂；
其中，a、b、c、d、e、f六种组分的重量份之和为100份，
其中式I的结构式：
Figure PCTCN2016083633-appb-000003
其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
其中，苯酚类物质的含量的测试方法：用电子天平称量2g的聚碳酸酯组合物后，将样品放入预设温度120℃并且温度均一稳定的恒温烘箱中2h后，放入索氏抽提装置进行甲醇抽提，抽提温度为85℃，时间为48h，将抽提液放置到恒温后，通过过滤网抽出20ul，以10ml/min的流速，借助流动相(甲醇:纯净水＝90:10)将抽提液进样到C18的吸附柱里进行分离以及定量，通过建立1ppm，5ppm，10ppm以及20ppm的标准溶液建立标准曲线后，可以通过标样的特定流出时间以及外推法计算得出苯酚类物质的含量。
优选地，如式I所述的苯酚类物质选自苯酚、对氯苯酚、2,4,6-三溴苯酚、长链烷基酚中的一种或几种。
优选地，如式II所述的位阻酚物质选自3,5-二叔丁基苯酚，优选为3-(3,5-二叔丁基-4-羟基苯基)丙酸十八醇酯。
其中，聚碳酸酯组合物中的如式I所述的苯酚类物质、如式II所述的位阻酚物质可以具有不同的重量百分比，聚碳酸组合物中如式I所述的苯酚类物质与如式II所述的位阻酚物质的重量百分比为0.001-20。
所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯，所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均 分子量16000-28000的芳香族聚碳酸酯。
所述橡胶改性的接枝聚合物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的接枝共聚物的一种或几种。
本体聚合法：包括溶胶，预聚合，聚合，脱挥和造粒五个步骤。将橡胶溶解在乙苯和苯乙烯中，按照配方量加入单体配成原料液，将配好的原料液输入预聚斧中进行预聚合，在聚合过程中，橡胶接枝单体，同时单体共聚，从溶液中分离出来，形成分散在原料液中连续相中的不连续相，当具有足够多的单体聚合后，不连续相的共聚物变成连续相，接枝的橡胶形成不连续相分散在连续的共聚物相中，完成相转变，最后经过进一步聚合，真空脱气，挤出，冷却和切粒得到最终制品；
本体-悬浮聚合法：按照配方调节橡胶和单体溶液，并同时加入聚合调节剂和自由基引发剂，将单体混合物在80℃-120℃进行本体聚合，聚合过程中不断搅拌，并将去离子水和悬浮剂加入到混合物中，使混合物得到分散，然后利用自由基催化剂进行悬浮聚合，得到一定聚合度后经过凝聚，过滤，洗涤，脱水和干燥后造粒获得制品。
乳液聚合法：橡胶通过在引发剂，去离子水，乳化剂和交联剂，聚合温度控制在50℃-80℃，将单体混合物加到橡胶乳胶进行接枝，最后进行洗涤，脱水和干燥后造粒获得制品。
其中，所述橡胶改性的接枝聚合物，按重量份计，选自包含如下b.1在b.2上的接枝聚合物：
b.1、5份-95份的b.1.1和b.1.2的混合物：
b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
b.2、5份-95份的聚丁二烯、聚异戊二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物、丙烯酰橡胶、有机硅氧烷橡胶的一种或几种。
其中，包括具有小于10℃，小于0℃，小于-10℃或者在-40℃到-80℃之间的Tg橡胶聚合物基底，和接枝到橡胶聚合物基底的刚性聚合物，适合用做橡胶的材料包括如共轭二烯等，刚性聚合物如苯乙烯，丙烯腈，丙烯酸酯等，烯烃橡胶如乙烯丙烯共聚物EPR或者乙烯丙烯二烯单体橡胶EPDM，乙烯-乙烯酸酯橡胶；硅酮橡胶；弹性体的甲基丙烯酸C1-8烷基酯，甲基丙烯酸C1-8烷基酯与丁二烯或者苯乙烯的弹性共聚物；或者包含至少一种上述弹性体的组合。适用刚性相的材料包括如单乙烯基芳香族单体，如苯乙烯和a-甲基苯乙烯和单乙烯基单体如丙烯腈、丙烯酸、甲基丙烯酸以及丙烯酸和甲基丙烯酸的C1-C6的酯，具体的是甲基丙烯酸甲酯。
优选地，所述橡胶改性的接枝聚合物选自苯乙烯-丁二烯-苯乙烯SBS、苯乙烯-丁二烯橡胶SBR、苯乙烯-乙烯-丁二烯-苯乙烯SEBS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA或甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS、以及苯乙烯-丙烯腈SAN形成的中的一种或几种，优选丙烯腈-丁二烯-苯乙烯接枝共聚物ABS；其中，MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
优选地，所述含磷阻燃剂选自磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A-双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
其中，所述协效阻燃剂选自含硅物质和/或含氟物质；所述含硅物质选自硅油、硅氧烷、硅氧烷共聚物中的一种或几种；所述含氟物质选自聚四氟乙烯和/或含有聚四氟乙烯的母粒。
硅氧烷共聚物是指包含聚二甲基硅氧烷嵌段，其中聚二甲基硅氧烷嵌段具有30-100个二甲基硅氧烷部分的聚合度，重复单元可以具有特定的嵌段长度并且能够使组合物在低温下具有相对好的韧性。
另外，上述聚碳酸酯组合物，还包括其它加工助剂，所述其它加工助剂选自稳定剂、增塑剂、脱模剂、填料、着色剂中的一种或几种。
合适的稳定剂包括有机亚磷酸酯，如亚磷酸三苯酯，亚磷酸三-(2,6-二甲基苯基)酯，亚磷酸三-壬基苯基酯，二甲基苯膦酸酯，磷酸三甲酯等，有机亚磷酸酯，烷基化的一元酚或者多元酚，多元酚和二烯的烷基化反应产物，对甲酚或者二环戊二烯的丁基化反应产物，烷基化的氢醌类，羟基化的硫代二苯基醚类，亚烷基-双酚，苄基化合物，多元醇酯类，苯并三唑类，二苯甲酮类的一种或者多种组合。
合适的增塑剂为邻苯二甲酸酯。
合适的脱模剂包括硬脂酸金属盐类，硬脂酸烷基酯类，硬脂酸季戊四醇酯类，石蜡，褐煤蜡等等。
合适的填料包括玻纤，玻璃粉，硅灰石，碳酸钙，硫酸钡，滑石粉，金属粉等等。
合适的着色剂包括各种颜料，染料如无机颜料的金属氧化物和混合金属氧化物的氧化锌，氧化钛，氧化铁，硫化物如硫化锌等；铝酸盐，硅酸盐，铬酸盐，铁酸盐等，炭黑，群青；有机颜料如偶氮类，重氮类，蒽醌类、蒽酮类、酞菁、喹啉类，萘，酮，嗪类等等。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)将如式I所述的苯酚类物质、如式II所述的位阻酚物质与聚碳酸酯在高混机中混合均匀，得到混合物料；
2)将混合物料与橡胶改性的接枝聚合物、阻燃剂、协效阻燃剂通过主喂料口加入双螺杆挤出机中，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
本发明的聚碳酸酯组合物可用于户外以及室内的应用领域，例如各种类型和尺寸的外壳部件，家用电器如电视机，打印机，modem外壳，显示器外壳等，或者在户外使用的汽车部件，建筑领域的外壳或者盖子，以及电器用具外壳和边框。
本发明与现有技术相比，具有如下有益效果：
本发明选用在聚碳酸酯组合物配方中添加特定含量的如式I所述的苯酚类物质以及如式II所述的位阻酚物质时，得到的聚碳酸酯组合物具有优异的耐溶剂性能和流动性，并能保持良好的热稳定性。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。
各性能的测试标准或方法：
苯酚类物质的含量的测试方法：用电子天平称量2g的聚碳酸酯组合物后，将样品放入预设温度120℃并且温度均一稳定的恒温烘箱中2h后，放入索氏抽提装置进行甲醇抽提，抽提温度为85℃，时间为48h，将抽提液放置到恒温后，通过过滤网抽出20ul，以10ml/min的流速，借助流动相(甲醇:纯净水＝90:10)将抽提液进样到C18的吸附柱里进行分离以及定量，通过建立1ppm，5ppm，10ppm以及20ppm的标准溶液建立标准曲线后，可以通过标样的特定流出时间以及外推法计算得出苯酚类物质的含量。
耐醇性(％)的测试方法：试验片的制备使用日精树脂工业株式会社制造的80吨注射成型机，在料筒温度280℃和模具温度80℃的条件下。将由上述方法制备的JIS1号哑铃型试验片在23℃的甲醇中浸泡7天。试验片浸泡处理前后的拉伸屈服强度按照JIS K7113的方法测定。求出“浸泡处理后试验片的拉伸屈服强度”对“浸泡处理前试验片的拉伸屈服强度”的比例(％)，以此作为耐醇性(％)。
加工缺陷的测试方法：通过注射成型制得尺寸为10cm(长)×4cm(宽)×1mm(厚)的模制品，并观察其外表(色调、表面状况)。色调不令人不悦且具有光滑和良好的表面状况的模制品可评估为“好”；而那些颜色难看或有着粗糙和差劲的表面状况的则可视为“差”。
流动长度(mm)的测试方式：在料筒温度280℃、注射压力74MPa和模具温度80℃的条件下，在厚度0.5mm和宽度40mm的平板形状的模具内将熔融树脂注射成型，对此时的流动长度进行测定，作为流动长度。而且，流动长度在基于注射成型的平板的宽度或厚度的各位置不为恒定的值时，将最大的流动长度与 最小的流动长度的和除以2得到的值作为流动长度。流动性越高的材料表现出越高的值。
热分解温度(℃)的测试方法：使用热重测定装置(PerkinElmer公司制，“TGA-7”)，在氮气氛下将组合物10mg以20℃/分钟从30℃升温至500℃。将相对于升温前的质量减少5wt％的温度作为热分解温度，热分解稳定越好其热稳定性越好。
本发明中使用的聚碳酸酯：
组分a-1：FN1900(日本出光)
组分a-2：H2200(日本三菱)
本发明中使用的如式I所述的苯酚类物质：
组分b：苯酚(上海TCI)；
本发明中使用的如式II所述的位阻酚物质：
组分c：3-(3,5-二叔丁基-4-羟基苯基)丙酸十八醇酯1076(BASF)；
本发明中使用的橡胶改性的接枝聚合物：
组分d-1：ABS 8391(上海高桥)
组分d-2：MBS EM500(韩国LG)
本发明中使用的阻燃剂：
组分e：BDP(艾迪科)
本发明中使用的协效阻燃剂：
组分f：PTFE(聚四氟乙烯)作为协效阻燃剂。
实施例1-9及对比例1-9：聚碳酸酯组合物的制备
按表1的配方将如式I所述的苯酚类物质、如式II所述的位阻酚物质与聚碳酸酯在高混机中混合均匀，得到混合物料；将混合物料与橡胶改性的接枝聚合物、阻燃剂、协效阻燃剂通过主喂料口加入双螺杆挤出机中，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物；测定聚碳酸酯组合物的耐醇性(％)、加工缺陷、流动长度和热分解温度性能指标，数据如表1所示。
表1实施例1-9及对比例1-9的具体配比(重量份)及其测试性能结果
Figure PCTCN2016083633-appb-000004
Figure PCTCN2016083633-appb-000005
续表1
Figure PCTCN2016083633-appb-000006
从表1的实施例和对比例的比较可以看出：本发明选用在聚碳酸酯组合物配方中添加特定含量的如式I所述的苯酚类物质以及如式II所述的位阻酚物质时， 得到的聚碳酸酯组合物具有优异的耐溶剂性能和流动性，并能保持良好的热稳定性。

Claims (15)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-86份的聚碳酸酯；
    b、0.0001份-1份如式I所述的苯酚类物质；
    c、0.01-5份如式II所述的位阻酚物质；
    d、8份-50份的橡胶改性的接枝聚合物；
    e、5份-25份的阻燃剂；
    f、0-10份的阻燃协效剂；
    其中，a、b、c、d、e、f六种组分的重量份之和为100份；
    其中式I的结构式：
    Figure PCTCN2016083633-appb-100001
    其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
    其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
  2. 一种如权利要求1所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-86份的聚碳酸酯；
    b、0.005份-0.2份如式I所述的苯酚类物质；
    c、0.03-1份如式II所述的位阻酚物质；
    d、8份-50份的橡胶改性的接枝聚合物；
    e、5份-25份的阻燃剂；
    f、0-10份的阻燃协效剂；
    其中，a、b、c、d、e、f六种组分的重量份之和为100份，
    其中式I的结构式：
    Figure PCTCN2016083633-appb-100002
    其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
    其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
  3. 一种如权利要求1或2所述的聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-86份的聚碳酸酯；
    b、0.01份-0.05份如式I所述的苯酚类物质；
    c、0.05-0.1份如式II所述的位阻酚物质；
    d、8份-50份的橡胶改性的接枝聚合物；
    e、5份-25份的阻燃剂；
    f、0-10份的阻燃协效剂；
    其中，a、b、c、d、e、f六种组分的重量份之和为100份，
    其中式I的结构式：
    Figure PCTCN2016083633-appb-100003
    其中R1和R5代表除了受阻基团以外的氢基，烷基，烷氧基，羟基，羧基或者羰基，酯基，R2，R3，R4代表含氢原子的取代基，优选氢原子；
    其中式II的分子式为CnOmR，其中n大于2，m大于2，R代表杂原子，优选N原子和S原子的长链取代基，更优选具有对称结构的含芳香基团的含N长链取代基。
  4. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，如式I所述的苯酚类物质选自苯酚、对氯苯酚、2,4,6-三溴苯酚、长链烷基酚中的一种或几种。
  5. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，如式II所述的位阻酚物质选自3,5-二叔丁基苯酚，优选为3-(3,5-二叔丁基-4-羟基苯基)丙酸十八醇酯。
  6. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，如式I所述的苯酚类物质与如式II所述的位阻酚物质的重量百分比为0.001-20。
  7. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯选自芳香族聚碳酸酯、脂肪族聚碳酸酯、芳香族-脂肪族聚碳酸酯、支化聚碳酸酯、硅氧烷共聚碳酸酯中的一种或几种；优选为芳香族聚碳酸酯，所述芳香族聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，优选为粘均分子量16000-28000的芳香族聚碳酸酯。
  8. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述橡胶改性的接枝聚合物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的接枝共聚物的一种或几种。
  9. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述橡胶改性 的接枝聚合物，按重量份计，选自包含如下b.1在b.2上的接枝聚合物：
    b.1、5份-95份的b.1.1和b.1.2的混合物：
    b.1.1、50份-95份的苯乙烯、苯乙烯衍生物如α-甲基苯乙烯、对苯甲基苯乙烯，二乙烯基苯乙烯，甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯、二甲基硅氧烷、苯基硅氧烷、多烷基硅氧烷的一种或几种；
    b.1.2、5份-50份的丙烯腈、甲基丙烯腈、甲基丙烯酸C1-C8-烷基酯、丙烯酸C1-C8-烷基酯的一种或几种；
    b.2、5份-95份的聚丁二烯、聚异戊二烯、苯乙烯-丁二烯无规共聚物及嵌段共聚物、丙烯腈-丁二烯无规共聚物及嵌段共聚物、聚丁二烯和聚异戊二烯共聚物、乙烯和a-烯烃共聚物、乙烯和a-不饱和羧酸酯共聚物、乙烯-丙烯-非共轭二烯三元共聚物、丙烯酰橡胶、有机硅氧烷橡胶的一种或几种。
  10. 根据权利要求9所述的聚碳酸酯组合物，其特征在于，所述橡胶改性的接枝聚合物选自苯乙烯-丁二烯-苯乙烯SBS、苯乙烯-丁二烯橡胶SBR、苯乙烯-乙烯-丁二烯-苯乙烯SEBS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA或甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS、以及苯乙烯-丙烯腈SAN形成的中的一种或几种，优选丙烯腈-丁二烯-苯乙烯接枝共聚物ABS；其中，MBS的粒径优选0.1um-0.5um，本体聚合法ABS粒径优选0.1um-2um，乳液聚合法ABS粒径优选0.05um-0.2um。
  11. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述阻燃剂选自卤系阻燃剂或无卤阻燃剂，优选无卤阻燃剂；所述卤系阻燃剂选自溴化聚苯乙烯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化苯乙烯-马来酸酐共聚物、溴化环氧树脂、溴化苯氧基树脂、十溴二苯醚、十溴代联苯、溴化聚碳酸酯、全溴三环十五烷或溴化芳香族交联聚合物的一种或几种，优选为溴化聚苯乙烯；所述无卤阻燃剂选自含氮阻燃剂、含磷阻燃剂或含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
  12. 根据权利要求11所述的聚碳酸酯组合物，其特征在于，所述含磷阻燃剂选自磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三二甲苯基酯、磷酸三(2,4,6-三甲基苯基)酯、磷酸三(2,4-二叔丁基苯基)酯、磷酸三(2,6-二叔丁基苯基)酯、间苯二酚双(磷酸二苯基酯)、对苯二酚双(磷酸二苯基酯)、双酚A- 双(磷酸二苯基酯)、间苯二酚双(2,6-二叔丁基苯基磷酸酯)、对苯二酚双(2,6-二甲基苯基磷酸酯)的一种或几种。
  13. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，所述协效阻燃剂选自含硅物质和/或含氟物质；所述含硅物质选自硅油、硅氧烷、硅氧烷共聚物中的一种或几种；所述含氟物质选自聚四氟乙烯和/或含有聚四氟乙烯的母粒。
  14. 根据权利要求1-3任一项所述的聚碳酸酯组合物，其特征在于，还包括其它加工助剂，所述其它加工助剂选自稳定剂、增塑剂、脱模剂、填料、着色剂中的一种或几种。
  15. 一种如权利要求1-14任一项所述的聚碳酸酯组合物的制备方法，其特征在于，包括如下步骤：
    1)将如式I所述的苯酚类物质、如式II所述的位阻酚物质与聚碳酸酯在高混机中混合均匀，得到混合物料；
    2)将混合物料与橡胶改性的接枝聚合物、阻燃剂、协效阻燃剂通过主喂料口加入双螺杆挤出机中，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0726101A (ja) * 1993-07-14 1995-01-27 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
CN1304427A (zh) * 1998-04-02 2001-07-18 通用电气公司 改善热稳定性的聚碳酸酯/橡胶改性接枝共聚物树脂的共混物
KR20060000706A (ko) * 2004-06-29 2006-01-06 현대자동차주식회사 복합 열가소성 플라스틱 시트 조성물
CN104893271A (zh) * 2015-05-27 2015-09-09 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0517565A (ja) * 1991-07-08 1993-01-26 Daicel Chem Ind Ltd ポリカーボネートの製造法
EP0884366A4 (en) * 1996-02-29 1999-05-06 Kaneka Corp FLAME RETARDANT THERMOPLASTIC RESIN COMPOSITION
MY121010A (en) * 1997-08-29 2005-12-30 Sabic Innovative Plastics Ip Polycarbonate resin composition
US6545089B1 (en) 1997-09-04 2003-04-08 General Electric Company Impact modified carbonnate polymer composition having improved resistance to degradation and improved thermal stability
DE102005058847A1 (de) 2005-12-09 2007-06-14 Bayer Materialscience Ag Polycarbonat-Formmassen
WO2012111718A1 (ja) * 2011-02-16 2012-08-23 三菱化学株式会社 ポリカーボネート樹脂組成物及び成形品
JP6019652B2 (ja) * 2011-03-31 2016-11-02 三菱化学株式会社 ポリカーボネート樹脂の製造方法
US8669315B2 (en) * 2011-08-22 2014-03-11 Sabic Innovative Plastics Ip B.V. Polycarbonate compositions and methods for the manufacture and use thereof
CN103772688A (zh) * 2013-12-24 2014-05-07 济南开发区星火科学技术研究院 一种聚碳酸酯的制备方法
CN104004330A (zh) * 2014-04-22 2014-08-27 上海奥塞尔化工科技有限公司 户外电信箱专用高耐候无卤阻燃pc/abs合金材料及制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0726101A (ja) * 1993-07-14 1995-01-27 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
CN1304427A (zh) * 1998-04-02 2001-07-18 通用电气公司 改善热稳定性的聚碳酸酯/橡胶改性接枝共聚物树脂的共混物
KR20060000706A (ko) * 2004-06-29 2006-01-06 현대자동차주식회사 복합 열가소성 플라스틱 시트 조성물
CN104893271A (zh) * 2015-05-27 2015-09-09 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法

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