WO2016188476A2 - 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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WO2016188476A2
WO2016188476A2 PCT/CN2016/083630 CN2016083630W WO2016188476A2 WO 2016188476 A2 WO2016188476 A2 WO 2016188476A2 CN 2016083630 W CN2016083630 W CN 2016083630W WO 2016188476 A2 WO2016188476 A2 WO 2016188476A2
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parts
resin
polycarbonate composition
flame retardant
group
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PCT/CN2016/083630
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French (fr)
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WO2016188476A3 (zh
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田征宇
孙东海
岑茵
佟伟
谢湘
刘贤文
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金发科技股份有限公司
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Priority to EP16799363.3A priority Critical patent/EP3305848B1/en
Priority to US15/576,852 priority patent/US10800915B2/en
Publication of WO2016188476A2 publication Critical patent/WO2016188476A2/zh
Publication of WO2016188476A3 publication Critical patent/WO2016188476A3/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
    • 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
    • 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
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method thereof.
  • Polycarbonate PC has high impact resistance and heat resistance. In order to improve its processing properties and sensitivity to notch impact, it is usually added to rubber-modified polymers such as ABS, MBS, etc., especially PC. PC/ABS alloys with ABS as the main raw material are widely used in the fields of electronic appliances, office supplies, and mobile phones. In recent years, the demand for miniaturization, weight reduction, and thinning has become more and more urgent. In order to meet these demands, Many improvements have been made in the material of polycarbonate compositions, such as adding more ABS resin and modifying ABS resin, reducing the molecular weight of PC resin, etc., but these measures will cause product defects and performance degradation. And problems such as reduced heat resistance.
  • the inventors have surprisingly found through extensive experimentation that the addition of the phenolic substance to the polycarbonate composition formulation is not more than 100 ppm based on the total weight of the polycarbonate composition, and the K value of the component I of the adjusted PC resin is 300,000.
  • the K value of -50000 and the component II is less than 300,000, the obtained polycarbonate composition has excellent heat resistance and fluidity, and is particularly suitable for a case where the use environment is relatively high.
  • 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 four components a, b, c, and d is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the four components a, b, c, d is 100 parts
  • the content of the phenolic substance in the total weight of the polycarbonate composition is 100 ppm or less;
  • the PC resin consists of one or more of the components I and/or II:
  • Component I PC resin having a K value of 300,000 to 500,000;
  • Component II an aromatic PC resin having a K value of less than 300,000;
  • R 1 and R 5 represent a hydrogen agent 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.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the four components a, b, c, d is 100 parts
  • the content of the phenolic substance in the total weight of the polycarbonate composition is 100 ppm or less;
  • the PC resin consists of one or more of the components I and/or II:
  • Component I PC resin having a K value of 300,000 to 500,000;
  • Component II an aromatic PC resin having a K value of less than 300,000;
  • R 1 and R 5 represent a hydrogen agent 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.
  • the K value is the injection flow index of the PC resin, the ratio of the viscosity average molecular weight to the terminal phenol group content, and the K value reflects the true fluidity of the PC resin, and the fluidity is the viscosity and distribution of the PC resin and the molecular chain.
  • the ends of the segments are formed in a proportional relationship.
  • the end group content of the resin is determined by in-situ infrared method, which can avoid the interference of moisture in the air and the moisture in the background and other hydroxyl-adsorbed substances.
  • the pressure is set to 10 -3 Pa, and the temperature program is heated from room temperature to 450 degrees. After 3-4 hours, the in-situ cell was placed in the infrared chamber for background scanning, and then pre-processed, and then the temperature was lowered to room temperature, and then the scanning spectrum was performed.
  • the infrared scanning was set to 64 scanning times and the resolution was 4 cm -1 .
  • the terminal hydroxyl group content is obtained by absorption peak.
  • the method for testing the content of the phenolic substance weighing a certain amount of the polycarbonate composition, performing Soxhlet extraction with methanol at 85 ° C, and then entering the styrene adsorption column at a constant flow rate at normal temperature, and A standard curve of different concentrations of standard phenolic substances was established, and the total phenolic content in the system was calculated according to the specific outflow time extrapolation method.
  • the percentage of the component I in the PC resin to the total weight of the PC resin is 50% by weight to 70% by weight; the component II The percentage by weight of the total weight of the PC resin is from 30% by weight to 50% by weight.
  • the content of the phenolic substance in the total weight of the polycarbonate composition is 80 ppm or less; preferably 50 ppm or less.
  • the content of the phenolic substance exceeds 100 ppm based on the total weight of the polycarbonate composition, under the action of heat and shear, the reversible unlocking reaction is caused, causing a series of hidden dangers of degradation of the polycarbonate, and the content of the phenolic substance exceeds 100 ppm also causes instability of the polymer end groups.
  • the component I has a K resin having a K value of from 320000 to 480000.
  • a carbonate precursor such as phosgene, a haloformate, a carbonate or an acid ester
  • the aromatic PC resin of the component II is selected from an aromatic PC resin prepared by a phosgene method and/or a melt method.
  • the rubber-modified graft polymer is selected from one or more of a rubber-modified graft polymer prepared by a bulk polymerization method, an emulsion polymerization method, or a bulk-suspension polymerization method.
  • Bulk polymerization method including sol, prepolymerization, polymerization, devolatilization and granulation.
  • the rubber is dissolved in ethylbenzene and styrene, and the monomer is mixed into a raw material liquid according to the formula amount, and the prepared raw material liquid is input.
  • Prepolymerization is carried out in a pre-polymerized axe.
  • the rubber grafting monomer while the monomer is copolymerized, is separated from the solution to form a discontinuous phase dispersed in the continuous phase of the raw material liquid, when there are enough single
  • the discontinuous phase of the copolymer becomes a continuous phase
  • the grafted rubber forms a discontinuous phase dispersed in the continuous copolymer phase, completes the phase transition, and finally undergoes further polymerization, vacuum degassing, extrusion, cooling and Pelletizing to obtain the 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;
  • the rubber modified graft polymer is selected from the group consisting of acrylonitrile-styrene copolymer AS, acrylonitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-acrylonitrile-butyl
  • styrene copolymer MABS acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene graft copolymer MBS; preferably acrylonitrile- Butadiene-styrene graft copolymer ABS; wherein the particle size of MBS is preferably 0.1 um to 0.5 um, the bulk particle size ABS particle size is preferably 0.1 um to 2 um, and the emulsion polymerization method ABS particle size is preferably 0.05 um to 0.2 um.
  • 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-trimethylphenyl phosphate).
  • ester tris(2,4-di-tert-butylphenyl) phosphate, tris(2,6-di-tert-butylphenyl) phosphate, resorcinol bis(diphenyl phosphate), p-benzene Diphenol bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate), hydroquinone bis ( One or more of 2,6-dimethylphenyl phosphate.
  • the other auxiliary agent of component d is selected from one or more of a stabilizer, a flame retardant synergist, an anti-drip agent, a lubricant, a mold release agent, a plasticizer, a filler, and a colorant.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethyl phosphite) Phenyl) ester, tri-decylphenyl phosphite, dimethyl phenylphosphonate, trimethyl phosphate, etc., organic phosphite, alkylated monohydric or polyhydric phenol, polyhydric phenol and diene Alkylation reaction product, butylated reaction product of p-cresol or dicyclopentadiene, alkylated hydroquinone, hydroxylated thiodiphenyl ether, alkylene-bisphenol, benzyl One or more combinations of compounds, polyol esters, benzotriazoles, benzophenones.
  • organic phosphites such as triphenyl phosphite, tris-(2,6-dimethyl phosphite) Phenyl) ester, tri-decyl
  • a suitable plasticizer is a phthalate.
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable colorants include various pigments, dyes.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the polycarbonate composition of the invention has excellent long-term thermal stability and weather resistance, no defects in appearance and excellent mechanical properties, and can be used in outdoor and indoor applications, such as various types and sizes of outer casing parts, household appliances. Such as televisions, printers, modem enclosures, display enclosures, etc., or automotive components for outdoor use, enclosures or covers for architectural applications, and electrical appliance enclosures and bezels.
  • the invention has the following beneficial effects:
  • the addition of the phenolic substance to the polycarbonate composition formulation is not more than 100 ppm based on the total weight of the polycarbonate composition, and the K value of the component I of the PC resin is adjusted to be 300,000 to 500,000 and the K of the component II.
  • the value is less than 300,000, the obtained polycarbonate composition has excellent heat resistance and fluidity, and is particularly suitable for applications where the use environment is relatively high.
  • Flowability (3mm, 1.5mm, 0.35mm) test method 1.0mm needle gate strip mold with injection temperature of 280 ° C, injection speed of 80%, injection pressure of 80% Long strips of different thicknesses are made, and finally the length of the strip after cooling is measured. The longer the length, the better the fluidity.
  • Test method for impact performance The test sample was obtained by an 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd., and obtained under the conditions of a cylinder temperature of 280 ° C and a mold temperature of 100 ° C, according to ASTM D265, using an Izod impact test. Machine (manufactured by Toyo Seiki Co., Ltd.), measuring the gap value of the Izod impact;
  • Test method for heat resistance using an 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd., and holding it at a cylinder temperature of 280 ° C for 5 minutes, and then injecting a polycarbonate composition, measuring the intrinsic viscosity before and after the injection, and evaluating the intrinsic viscosity. Stability. The smaller the absolute value of the difference between the "intrinsic viscosity after injection” and the “intrinsic viscosity after injection”, the more preferable.
  • the evaluation when the absolute value of the difference is less than 0.03 dl/g, the evaluation is "good (G)", and when the absolute value of the difference is 0.03 dl/g or more and less than 0.10 dl/g, the evaluation is "medium (M)”. When the absolute value of the difference was 0.10 dl/g or more, the evaluation was “poor (NG)".
  • the PC resin used in the present invention is prepared as follows:
  • Component a-1 PC resin having a K value of 300,000 to 500,000, which is prepared by an interfacial polycondensation method, a bisphenol in sodium hydroxide, and a carbonate precursor dissolved in methylene chloride (such as phosgene, halogen).
  • the carbamate, carbonate or acid ester reacts at the phase interface in the presence of the catalyst triethylamine to form a low molecular weight polycarbonate.
  • the m/a ratio is 0.5 by adjusting the pH to 11.
  • the conditions are then further polycondensed by reaction time to produce a polycarbonate product of a specific K value.
  • PC1-1 is a PC resin, and the K value is 300,000;
  • PC1-2 is a PC resin with a K value of 320000;
  • PC1-3 is PC resin, K value is 500000;
  • Component a-2 an aromatic PC resin having a K value of less than 300,000;
  • PC2-1 is an aromatic PC resin, the K value is 250,000, and the percentage of the total weight of the PC resin is 30% by weight; the preparation method thereof: reacting at the phase interface in the presence of the catalyst triethylamine to form a low molecular polycarbonate, The polycarbonate final product having a specific K value of 250,000 was further polycondensed by the reaction time by the pH adjustment to 11 under the condition of an m/a ratio of 0.3.
  • K value is 600000; preparation method: reacting at the phase interface in the presence of the catalyst triethylamine to form a low molecular polycarbonate, and the m/a ratio is 0.8 by adjusting the pH to 11.
  • the polycarbonate final product having a K value of 600,000 was then obtained by the reaction time under the conditions.
  • Phenolic substances used in the present invention are used in the present invention:
  • Rubber modified graft polymer used in the present invention Rubber modified graft polymer used in the present invention:
  • Component b-1 ABS2 bulk polymerization method 8391 (Shanghai Gaoqiao);
  • Component b-2 ABS1 emulsion polymerization method 757 (Chi Mei, Taiwan);
  • Component b-3 MBS EM500 (LG, Korea);
  • Component c BDP, bisphenol A-bis(diphenyl phosphate) (Idico);
  • Component d-1 PTFE (polytetrafluoroethylene) as an anti-drip agent
  • Component d-2 PETS (pentaerythritol stearate) as a release agent.
  • the phenolic substance is combined with dimethyl siloxane to form a phenolic substance pretreatment solution with a mass fraction of 0.20 ppm-350 ppm; the phenolic substance pretreatment solution is blended with the PC resin in a high-mixer to obtain Pretreated PC resin; according to the formulation of Table 1, the pretreated PC resin, rubber modified graft polymer, flame retardant, other additives are weighed according to the ratio, and then blended by high mixer or mixer. , extrusion, water cooling, granulation to obtain columnar granules of the polycarbonate composition.
  • the present invention selects a group in which the phenolic substance is added to the polycarbonate composition formulation based on the total weight of the polycarbonate composition not exceeding 100 ppm, and the PC resin is adjusted.
  • the K value of the fraction I is from 300,000 to 500,000 and the K value of the component II is less than 300,000, the obtained polycarbonate composition has excellent heat resistance and fluidity, and is particularly suitable for applications where the use environment is relatively high.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明公开了一种聚碳酸酯组合物，按重量份计，包括以下组成： a、30份‐87份的PC树脂； b、8份‐50份的橡胶改性的接枝聚合物； c、5份‐25份的阻燃剂； d、0‐10份的其它助剂；其中，a、b、c、d四种组分的重量份之和为100份。本发明选用在聚碳酸酯组合物配方中添加苯酚类物质基于聚碳酸酯组合物的总重量中不超过100ppm，以及调整PC树脂的组分I的K值为300000‐500000和组分II的K值小于300000时，得到的聚碳酸酯组合物具有优异的耐热性和流动性，特别适用于使用环境要求比较高的场合；其中苯酚类物质的结构式如式(1)：其中R1和R5代表除了受阻基团以外的氢剂，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。

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具有较高耐冲击性及耐热性等特性，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合金被广泛应用于电子电器、办公室用品，手机行业等领域，近年来，小型化、轻量化和薄壁化的需求越来越迫切，为了满足这些需求，在聚碳酸酯组合物材料方面做了许多改进，如添加更多含量的ABS树脂以及对ABS树脂进行改性，降低PC树脂分子量等等，但是这些举措或多或少都会引起产品的残缺，性能衰减以及耐热性降低等问题。
到目前为止，关于苯酚类物质以及PC树脂的K值对所述聚碳酸酯组合物的耐热性以及流动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苯酚类物质基于聚碳酸酯组合物的总重量中不超过100ppm，以及调整PC树脂的组分I的K值为300000-500000和组分II的K值小于300000时，得到的聚碳酸酯组合物具有优异的耐热性和流动性，特别适用于使用环境要求比较高的场合。
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热性和流动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-87份的PC树脂；
b、8份-50份的橡胶改性的接枝聚合物；
c、5份-25份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份。
优选地，一种聚碳酸酯组合物，按重量份计，包括以下组成：
a、35份-75份的PC树脂；
b、8份-35份的橡胶改性的接枝聚合物；
c、5份-20份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份，
基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于100ppm；
所述PC树脂由组分I和/或组分II中的一种或多种混合物组成：
组分I：K值为300000-500000的PC树脂；
组分II：K值为小于300000的芳香族PC树脂；
其中苯酚类物质的结构式如式(1)：
Figure PCTCN2016083630-appb-000001
式(1)
其中R1和R5代表除了受阻基团以外的氢剂，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。
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、42份-70份的PC树脂；
b、8份-30份的橡胶改性的接枝聚合物；
c、5份-18份的阻燃剂；
d、0-10份的其它助剂；
其中，a、b、c、d四种组分的重量份之和为100份，
基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于100ppm；
所述PC树脂由组分I和/或组分II中的一种或多种混合物组成：
组分I：K值为300000-500000的PC树脂；
组分II：K值为小于300000的芳香族PC树脂；
其中苯酚类物质的结构式如式(1)：
Figure PCTCN2016083630-appb-000002
式(1)
其中R1和R5代表除了受阻基团以外的氢剂，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，所述K值为PC树脂的注塑流动指数，粘均分子量与端酚基含量的比值，K值反映PC树脂的真实流动性，其流动性是与PC树脂的粘度及其分布以及分子链段的端部组成成正比关系。其中，树脂的粘均分子量[Mv]是指通过用乌氏粘度计在20℃下使用氯甲烷作为溶剂的测量确定特性粘度[η](单位：dl/g)，然后通过Schnell粘度方程即η＝1.23×10-4Mv0.83计算得到的值。树脂的端基含量通过原位红外法测定，可以避免空气中的水分以及背景中的水分和其它羟基吸附的物质的干扰，压力设置为10-3Pa，升温程序从室温加热到450度后恒温3-4小时，将原位池放入红外仓进行背景扫描后，进行预处理，然后将温度降到室温后进行扫描谱图，红外扫描设置为扫描次数为64，分辨率为4cm-1.通过吸收峰得到末端羟基含量。其中，苯酚类物质的含量的测试方法：称量一定量的聚碳酸酯组合物，用85℃的甲醇进行索氏抽提，然后在常温中以一定的流速进入苯乙烯类吸附谱柱，并建立不同浓度的标准苯酚类物质溶液的标准曲线，根据特定流出时间外推法来算体系中总苯酚类物质的含量。
所述PC树脂中组分I占PC树脂总重量的百分比为50wt％-70wt％；组分II 占PC树脂总重量的百分比为30wt％-50wt％。
基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于80ppm；优选为小于等于50ppm。当基于聚碳酸酯组合物的总重量中苯酚类物质的含量超过100ppm，在热和剪切的作用下，导致可逆解锁反应，造成聚碳酸酯的降解产生一系列隐患，另外苯酚类物质含量超过100ppm，也会造成聚合物端基的不稳定。
优选地，所述组分I的K值为320000-480000的PC树脂。
上述K值为300000-500000的PC树脂的制备方法：二羟基化合物与碳酸盐前体(如光气，卤代甲酸酯，碳酸盐或者酸酯)并通常在受酸体与分子量调节剂的存在下反应而生产。
所述组分II的芳香族PC树脂选自光气法和/或熔融法制备的芳香族PC树脂。
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-悬浮聚合法制备的橡胶改性的接枝聚合物的一种或几种。
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。
优选地，所述橡胶改性的接枝聚合物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；优选为丙烯腈-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。
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。
所述组分d的其它助剂选自稳定剂、阻燃增效剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、着色剂的一种或几种。
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。
合适的着色剂包括各种颜料，染料。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)将苯酚类物质与二甲基硅氧烷配成质量分数为0.20ppm-350ppm的苯酚类物质预处理溶液；
2)将苯酚类物质预处理溶液与PC树脂在高混机中进行共混，得到预处理的PC树脂；
3)将预处理的PC树脂、橡胶改性的接枝聚合物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，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由于具有优异的长期热稳定性和耐候性，外观无缺陷以及优异的力学性能，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苯酚类物质基于聚碳酸酯组合物的总重量中不超过100ppm，以及调整PC树脂的组分I的K值为300000-500000和组分II的K值小于300000时，得到的聚碳酸酯组合物具有优异的耐热性和流动性，特别适用于使用环境要求比较高的场合。
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：
苯酚类物质含量的测定方法：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；
流动性(3mm、1.5mm、0.35mm)的测试方法：点浇口为1.0mm的针形浇口长条模具，在注射温度为280℃，注射速度为80％，注射压力为80％的方式制成不同厚度的长条，最后测冷却后长条的长度，长度越长，流动性越好。
冲击性能的测试方法：测试样条通过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100℃的条件下得到后，按照ASTM D265，使用艾佐德冲击试验机(株式会社东洋精机制作所制造)，测定带缺口的艾佐德冲击值；
耐热性的测试方式：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℃下滞留5分钟，然后注射聚碳酸酯组合物，测定注射前后的特性粘度，评价特性粘度的稳定性。“注射后的特性粘度”和“注射前的特性粘度”的差的绝对值越小越优选。这里，差的绝对值低于0.03dl/g时，评价为“良好(G)”，差的绝对值为0.03dl/g以上、低于0.10dl/g时，评价为“中等(M)”，差的绝对值为0.10dl/g以上时，评价为“不良(NG)”。
本发明中使用的PC树脂按照下述方法制备：
组分a-1：K值为300000-500000的PC树脂，其制备方法：采用界面缩聚法，在氢氧化钠的双酚和溶于二氯甲烷的碳酸盐前体(如光气，卤代甲酸酯，碳酸盐或者酸酯)，在催化剂三乙胺的存在下在相界面发生反应生成低分子的聚碳酸酯，通过pH值调整到11的条件下，m/a比为0.5的条件下然后通过反应时间来进一步缩聚生成特定K值的聚碳酸酯终产物。
其中：
PC1-1为PC树脂，K值为300000；
PC1-2为PC树脂，K值为320000；
PC1-3为PC树脂，K值为500000；
组分a-2：K值为小于300000的芳香族PC树脂；
其中，
PC2-1为芳香族PC树脂，K值为250000，占PC树脂总重量的百分比为30wt％；其制备方法：在催化剂三乙胺的存在下在相界面发生反应生成低分子的聚碳酸酯，通过pH值调整到11的条件下，m/a比为0.3的条件下然后通过反应时间来进一步缩聚生成特定K值250000的聚碳酸酯终产物。
组分a-3：
PC3-1，K值为600000；其制备方法：在催化剂三乙胺的存在下在相界面发生反应生成低分子的聚碳酸酯，通过pH值调整到11的条件下，m/a比为0.8的条件下然后通过反应时间得到K值为600000的聚碳酸酯终产物。
本发明中使用的苯酚类物质：
苯酚：(上海TCI)；
对甲基苯酚类物质：(阿拉丁)；
二甲基苯酚类物质：(阿拉丁)；
本发明中使用的橡胶改性的接枝聚合物：
组分b-1：ABS2 本体聚合法8391(上海高桥)；
组分b-2：ABS1 乳液聚合法757(台湾奇美)；
组分b-3：MBS  EM500(韩国LG)；
本发明中使用的阻燃剂：
组分c：BDP，双酚A-双(磷酸二苯基酯)(艾迪科)；
本发明中使用的其它助剂：
组分d-1：PTFE(聚四氟乙烯)作为抗滴落剂；
组分d-2：PETS(季戊四醇硬脂酸酯)作为脱模剂。
实施例1-9及对比例1-9：聚碳酸酯组合物的制备
将苯酚类物质与二甲基硅氧烷配成质量分数为0.20ppm-350ppm的苯酚类物质预处理溶液；将苯酚类物质预处理溶液与PC树脂在高混机中进行共混，得到 预处理的PC树脂；按表1的配方将预处理的PC树脂、橡胶改性的接枝聚合物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，挤出，过水冷却，造粒得到柱状颗粒的聚碳酸酯组合物。
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 PCTCN2016083630-appb-000003
续表1
Figure PCTCN2016083630-appb-000004
Figure PCTCN2016083630-appb-000005
其中：-代表无法正常测试流动性
从表1的实施例及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苯酚类物质基于聚碳酸酯组合物的总重量中不超过100ppm，以及调整PC树脂的组分I的K值为300000-500000和组分II的K值小于300000时，得到的聚碳酸酯组合物具有优异的耐热性和流动性，特别适用于使用环境要求比较高的场合。

Claims (14)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-87份的PC树脂；
    b、8份-50份的橡胶改性的接枝聚合物；
    c、5份-25份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份。
  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、35份-75份的PC树脂；
    b、8份-35份的橡胶改性的接枝聚合物；
    c、5份-20份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份，
    基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于100ppm；
    所述PC树脂由组分I和/或组分II中的一种或多种混合物组成：
    组分I：K值为300000-500000的PC树脂；
    组分II：K值为小于300000的芳香族PC树脂；
    其中苯酚类物质的结构式如式(1)：
    Figure PCTCN2016083630-appb-100001
    其中R1和R5代表除了受阻基团以外的氢剂，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。
  3. 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、42份-70份的PC树脂；
    b、8份-30份的橡胶改性的接枝聚合物；
    c、5份-18份的阻燃剂；
    d、0-10份的其它助剂；
    其中，a、b、c、d四种组分的重量份之和为100份，
    基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于100ppm；
    所述PC树脂由组分I和/或组分II中的一种或多种混合物组成：
    组分I：K值为300000-500000的PC树脂；
    组分II：K值为小于300000的芳香族PC树脂；
    其中苯酚类物质的结构式如式(1)：
    Figure PCTCN2016083630-appb-100002
    其中R1和R5代表除了受阻基团以外的氢剂，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。
  4. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述PC树脂中组分I占PC树脂总重量的百分比为50wt％-70wt％；组分II占PC树脂总重量的百分比为30wt％-50wt％。
  5. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，基于聚碳酸酯组合物的总重量中苯酚类物质的含量小于等于80ppm；优选为小于等于50ppm。
  6. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述组分I的K值为320000-480000的PC树脂。
  7. 根据权利要求2或3所述的聚碳酸酯组合物，其特征在于，所述组分II的芳 香族PC树脂选自光气法和/或熔融法制备的芳香族PC树脂。
  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-悬浮聚合法制备的橡胶改性的接枝聚合物的一种或几种。
  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丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯接枝共聚物ABS、甲基丙烯酸甲酯-丙烯腈-丁二烯苯乙烯共聚物MABS、丙烯腈-苯乙烯-丙烯酸三元共聚物ASA、甲基丙烯酸甲酯-丁二烯-苯乙烯接枝共聚物MBS中的一种或几种；优选为丙烯腈-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，所述组分d的其它助剂选自稳定剂、阻燃增效剂、抗滴落剂、润滑剂、脱模剂、增塑剂、填料、着色剂的一种或几种。
  14. 一种如权利要求1-13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)将苯酚类物质与二甲基硅氧烷配成质量分数为0.20ppm-350ppm的苯酚类物质预处理溶液；
    2)将苯酚类物质预处理溶液与PC树脂在高混机中进行共混，得到预处理的PC树脂；
    3)将预处理的PC树脂、橡胶改性的接枝聚合物、阻燃剂、其它助剂按照比例称量后，通过高混机或者混合机完成共混，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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