WO2016188475A1 - 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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WO2016188475A1
WO2016188475A1 PCT/CN2016/083624 CN2016083624W WO2016188475A1 WO 2016188475 A1 WO2016188475 A1 WO 2016188475A1 CN 2016083624 W CN2016083624 W CN 2016083624W WO 2016188475 A1 WO2016188475 A1 WO 2016188475A1
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polycarbonate
parts
polycarbonate composition
ppm
flame retardant
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French (fr)
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岑茵
何继辉
孙东海
佟伟
谢湘
郭唐华
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Kingfa Science and Technology Co Ltd
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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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

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 alloy with ABS as the main raw material is an important engineering plastic, which can combine the excellent performance of both, and improve the physical properties and processing performance.
  • ABS due to the addition of ABS, the double bond in the system will bring long-term Thermal oxygen aging performance and weathering performance hazards, especially where the use environment is relatively high.
  • WO 99/11713 A1 discloses an improved moisture resistance and at the same time a high mechanical level of flame retardant PC/ABS, characterized in that the graft polymer has an alkali metal content of less than 1 ppm.
  • WO 2007/009622 A1 discloses a composition containing polycarbonate and ABS and having a low lithium ion content with impact modification with improved hydrolysis resistance, which is added with low lithium ions in a graft polymer prepared by bulk or emulsion method.
  • the composition of the composition has significantly better hydrolysis resistance than the higher lithium ion content composition.
  • the inventors have surprisingly found through extensive experimentation that the addition of a phenolic substance to the polycarbonate composition formulation is not more than 20 ppm based on the total weight of the polycarbonate composition, and the total amount of the metal zinc element and the manganese element is based on the total amount of the compound.
  • the total weight of the polycarbonate composition is not more than 200 ppm, the obtained polycarbonate composition has excellent high-temperature and high-humidity stability and mechanical properties, and is particularly suitable for applications where the use environment is relatively high.
  • Still 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 1 ppm or more and 20 ppm or less;
  • the total amount of metal zinc element and manganese element in the total weight of the polycarbonate composition is not more than 200 ppm;
  • 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.
  • the test method for the content of phenolic substances weighing 2 g of polycarbonate combination with an electronic balance
  • the sample was placed in a constant temperature oven at a preset temperature of 120 ° C and the temperature was uniformly stabilized, and then placed in a Soxhlet extraction device for methanol extraction, the extraction temperature was 85 ° C, the time was 48 h, and the extract was extracted.
  • Test method for the content of metallic zinc and manganese metal elements ICP-MS mixed standard method.
  • the content of the phenolic substance in the total weight of the polycarbonate composition is 10 ppm or more and 2 ppm or more; more preferably 8 ppm or more and 3 ppm or more.
  • the total amount of the metal zinc element and the manganese element in the total weight of the polycarbonate composition is not more than 100 ppm, more preferably not more than 50 ppm.
  • the total amount of the metal zinc element and the manganese element is more than 200 ppm based on the total weight of the polycarbonate composition, coloring is introduced, which affects the color of the light colored article and limits its application to light colored articles.
  • the compounding weight ratio of the metal zinc element to the manganese element in the total weight of the polycarbonate composition is from 0.2 to 20; preferably from 1 to 10; more preferably from 1.5 to 5.
  • 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 Aromatic polycarbonate.
  • the aromatic polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, and preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000.
  • the viscosity average molecular weight was calculated by using a solution of dichloromethane as a solvent at a test temperature of 25 ° C.
  • the above polycarbonate can be produced by an interfacial polymerization method and a transesterification method, and the terminal hydroxyl group content can be controlled in the process.
  • the ABS resin is selected from one or more of ABS resins prepared by bulk polymerization, bulk-suspension polymerization, and emulsion polymerization; wherein the bulk polymerization ABS particle size is preferably 0.1 um to 2 um, and the emulsion polymerization method is ABS.
  • the particle size is preferably 0.05 um to 0.2 um.
  • Bulk polymerization including sol, prepolymerization, polymerization, devolatilization and granulation in five steps: dissolving the rubber In ethylbenzene and styrene, the monomer is formulated into a raw material liquid according to the formula amount, and the prepared raw material liquid is input into the pre-polymerization kettle for pre-polymerization.
  • the rubber grafting monomer and the monomer are copolymerized. Separated from the solution to form a discontinuous phase dispersed in the continuous phase of the raw material liquid.
  • the discontinuous phase of the copolymer becomes a continuous phase, and the grafted rubber forms a discontinuous phase dispersion.
  • the phase transition is completed, and finally 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 formulation, and notify the addition of 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, and then granulating 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 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 bromine Bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate Or one or more of perfluorotricyclopentadecane 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 resistors
  • One or more of a flammant or a flame retardant containing nitrogen and phosphorus is
  • 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 other auxiliary agent in the polycarbonate composition is selected from the group consisting of a toughening agent, a stabilizer, a flame retardant synergist, an anti-drip agent, a lubricant, a mold release agent, a plasticizer, a filler, a colorant or Several.
  • 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, p-cresol or The butylated reaction product of dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzo One or more combinations of triazoles, benzophenones.
  • 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 colorants include various pigments, dyes.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • a manganese-containing compound and a zinc-containing compound and a phenylsiloxane are formulated into a phenylsiloxane solution having a mass fraction of from 0.15 ppm to 300 ppm;
  • the manganese-containing compound is one or more selected from the group consisting of manganese dioxide, manganese chloride, manganese nitrate, manganese carbonate, and manganese sulfate; and the zinc-containing compound is selected from the group consisting of zinc chloride, zinc sulfate, and zinc nitrate.
  • zinc carbonate and zinc sulfide is one or more selected from the group consisting of zinc carbonate and zinc sulfide.
  • the polycarbonate containing a phenolic substance can obtain a polycarbonate resin containing a different content of a phenolic substance by a different synthesis method, thereby realizing a residual phenolic substance content in the final polycarbonate composition.
  • the polycarbonate composition of the invention has excellent long-term heat and humidity aging resistance, processing stability and mechanical properties, can be used for a long time under high temperature and high humidity without failure, and can be used for outdoor and indoor applications, such as various types. And size housing components, household appliances such as televisions, printers, modem housings, display housings, etc., or automotive components for outdoor use, enclosures or covers for architectural applications, and electrical appliance housings and bezels.
  • the invention has the following beneficial effects:
  • the phenolic material in the polycarbonate composition formulation of the present invention is based on the total of the polycarbonate composition. Not more than 20 ppm by weight, and the total amount of metal zinc element and manganese element is not more than 200 ppm based on the total weight of the polycarbonate composition, passing trace amounts of phenolic substances and trace amounts of metallic zinc and manganese
  • the synergistic effect of the compounding provides the polycarbonate composition with excellent high-temperature and high-humidity stability and mechanical properties, and is particularly suitable for applications where the use environment is relatively high.
  • Test method for metal zinc content and metal manganese content ICP-MS mixed standard method
  • N1 represents the intrinsic viscosity of 0h before aging
  • N2 represents the intrinsic viscosity measured after a certain period of time (100h, 500h) of double 85 damp heat aging.
  • Measurement method of 150 ° C impact performance retention rate 500 h: The test sample was obtained by 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 100 ° C, in accordance with ASTM D265.
  • the Izod impact tester manufactured by Toyo Seiki Co., Ltd.
  • the test method measures the Izod impact value after aging, according to the retention rate
  • the formula yields a 150°C impact performance retention rate. The larger the value, the better the performance.
  • Component a-1 PC phenolic substance content is 8 ppm
  • preparation method adding a quantitative aqueous solution of NaOH to the liquid phase phenolic substance for interfacial polymerization to obtain intermediate product DPC, and then controlling the residual amount of phenolic substance by washing to 8 ppm and Bisphenol A is obtained by melt transesterification to give the final product.
  • Component a-2 PC phenolic substance content is 18 ppm
  • preparation method adding a quantitative aqueous solution of NaOH to the liquid phase phenolic substance for interfacial polymerization to obtain intermediate product DPC, and then controlling the residual amount of phenolic substance by washing to 18 ppm and Bisphenol A is obtained by melt transesterification to give the final product.
  • Component a-3 PC phenolic substance content is 60 ppm
  • preparation method adding a quantitative aqueous solution of NaOH to the liquid phase phenolic substance for interfacial polymerization to obtain intermediate product DPC, and then controlling the residual amount of phenolic substance by washing to 60 ppm and Bisphenol A is obtained by melt transesterification to give the final product.
  • ABS resin used in the present invention is ABS resin used in the present invention:
  • Component b-1 ABS 8391 (Shanghai Gaoqiao)
  • Component b-2 ABS 757 (Taiwan Chi Mei)
  • Component c-1 BDP (bisphenol A-bis (triphenyl phosphate), Edico;
  • Component c-2 RDP (resorcinol-bis(diphenyl phosphate), Zhejiang Wansheng;
  • Component c-3 TPP (triphenyl phosphate), Tianjin Beyond;
  • Component d-1 AO168: tris[2.4-di-tert-butylphenyl]phosphite as stabilizer; (BASF)
  • Component d-2 PETS: as a lubricant (Longsha, USA)
  • Component d-3 PTFE: Polytetrafluoroethylene as an anti-drip agent (Guangzhou entropy energy).
  • the manganese-containing compound and the zinc-containing compound and the phenylsiloxane are formulated into a phenylsiloxane solution having a mass fraction of 0.15 ppm to 300 ppm; and the phenylsiloxane solution is contained in an amount of 8 ppm to 60 ppm.
  • Polycarbonate of phenolic substance is blended in a high-mixer to obtain a pretreated polycarbonate; after pre-treated polycarbonate, graft copolymer, flame retardant, and other auxiliary agents are weighed in proportion, Blending, extrusion, water cooling, granulation to obtain columnar granules of polycarbonate composition by high mixer or mixer; viscosity ratio (100h, 150h) to polycarbonate composition and impact performance retention rate ( 150h) Test, the data is shown in Table 1.
  • the phenolic substance in the polycarbonate composition formulation is not more than 20 ppm based on the total weight of the polycarbonate composition, and the complex of the metal zinc element and the manganese element.
  • the total amount is not more than 200 ppm based on the total weight of the polycarbonate composition, the obtained polycarbonate composition has excellent high-temperature and high-humidity stability and mechanical properties.

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  • Health & Medical Sciences (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份的聚碳酸酯； b、8份‐50份的ABS树脂； c、2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。本发明选用聚碳酸酯组合物配方中的苯酚类物质基于聚碳酸酯组合物的总重量中不超过20ppm，以及金属锌元素与锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过200ppm时，得到的聚碳酸酯组合物具有优异的高温高湿性能稳定性和机械性能，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。

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，但是由于ABS的加入，体系中双键会带来长期热氧老化性能以及耐候性能的隐患，特别是对使用环境要求比较高的场合。
WO 99/11713A1公开了改进的抗湿性能并同时具有高机械水平的阻燃PC/ABS，其特征在于该接枝聚合物中具有小于1ppm的碱金属含量。
WO 2007/009622A1公开了含有聚碳酸酯和ABS并具有低锂离子含量的组合物具有改进抗水解性的抗冲改性，其通过本体法或者乳液法制备的接枝聚合物中添加低锂离子含量的组合物抗水解性能明显好于较高锂离子含量的组合物。
但是到目前为止，关于苯酚类物质以及金属锌元素与锰元素的复配总量对所述聚碳酸酯组合物能在高温高湿环境下性能保持稳定还未见报道。
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20ppm，以及金属锌元素与锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过200ppm时，得到的聚碳酸酯组合物具有优异的高温高湿性能稳定性和机械性能，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高温高湿性能稳定性和机械性能的聚碳酸酯组合物。
本发明的再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份的聚碳酸酯；
b、8份-50份的ABS树脂；
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、44份-75份的聚碳酸酯；
b、8份-30份的ABS树脂；
c、5份-18份的阻燃剂；
d、0.1-8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大于等于1ppm和小于等于20ppm；
基于聚碳酸酯组合物的总重量中金属锌元素与锰元素的复配总量不超过200ppm；
其中苯酚类物质的结构式如式(1)：
Figure PCTCN2016083624-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，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；
金属锌元素和金属锰元素的含量的测试方法：ICP-MS混标法。
优选地，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10ppm和大于等于2ppm；更优选为小于等于8ppm和大于等于3ppm。
如果苯酚类物质残留量太多，特别是超过20ppm的情况下，在后续加工过程中会产生如长期湿热老化粘度变化大，导致性能大幅度下降的隐患。
优选地，基于聚碳酸酯组合物的总重量中金属锌元素与锰元素的复配总量不超过100ppm，更优选不超过50ppm。当基于聚碳酸酯组合物的总重量中金属锌元素与锰元素的复配总量超过200ppm，会引入色污，对浅色制品的颜色有影响，限制其在浅色制品方面的应用。
其中，基于聚碳酸酯组合物的总重量中金属锌元素与锰元素的复配重量比为0.2-20；优选为1-10；更优选为1.5-5。
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。当粘均分子量在上述范围内，机械强度良好并且能保持优异的成型性。其中，粘均分子量是通过使用二氯甲烷作为溶剂在测试温度为25℃的溶液粘度计算出来的。
上述聚碳酸酯的制备方法可以通过界面聚合法和酯交换法制得，并且可以在过程中控制端羟基的含量。
其中，所述ABS树脂选自本体聚合法、本体-悬浮聚合法、乳液聚合法制备的ABS树脂的一种或几种；其中，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。
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釜中进行预聚合，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，并通知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。
该聚碳酸酯组合物中的其它助剂选自增韧剂、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)将含锰化合物以及含锌化合物与苯基硅氧烷配成质量分数为0.15ppm-300ppm的苯基硅氧烷溶液；
2)将该苯基硅氧烷溶液与含有8ppm-60ppm苯酚类物质的聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；
3)将预处理的聚碳酸酯、接枝共聚物、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。
其中，所述含锰化合物选自二氧化锰、氯化锰、硝酸锰、碳酸锰、硫酸锰中的一种或几种；所述含锌化合物选自氯化锌、硫酸锌、硝酸锌、碳酸锌、硫化锌中的一种或几种。
所述含有苯酚类物质的聚碳酸酯，通过不同合成方法得到含有不同含量的苯酚类物质的聚碳酸酯树脂，从而实现最终聚碳酸酯组合物中残留苯酚类物质含量。其中，最终聚碳酸酯组合物中残留苯酚类物质含量的计算方法为：聚碳酸酯配方的质量百分比*含有苯酚类物质的聚碳酸酯的苯酚类物质含量＝聚碳酸酯组合物的残留苯酚类物质含量。
本发明的聚碳酸酯组合物由于具有优异的耐长期湿热老化性能，加工稳定性以及机械性能都能在高温高湿下长期使用不出现失效，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：
本发明选用聚碳酸酯组合物配方中的苯酚类物质基于聚碳酸酯组合物的总 重量中不超过20ppm，以及金属锌元素与锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过200ppm时，通过痕量的苯酚类物质和痕量的金属锌元素与锰元素复配的协同作用，得到的聚碳酸酯组合物具有优异的高温高湿性能稳定性和机械性能，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；
金属锌元素含量和金属锰元素含量的测试方法：ICP-MS混标法；
双85测试后粘度比值(100h、500h)的测定方法：GB/T1632称量粒料并放入湿度为85％温度为85℃的恒温恒湿老化箱，每隔一段时间取出2g，用氯仿溶解后经过乌氏粘度计测得粘度，按照以下公式算出粘度比：
(N1-N2)/N1
N1代表老化前0h的特性粘度；N2代表双85湿热老化一定时间后(100h、500h)测得的特性粘度，粘度比数值越大，代表稳定性越差，反之，数值越小，代表稳定性越好。
150℃冲击性能保持率(500h)的测定方法：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，通过样条放入预设温度为150℃的恒温烘箱老化500h后，根据前述的测试方法测得老化后的艾佐德冲击值，根据保持率的计 算公式得到150℃冲击性能保持率，数值越大，性能保持越好。
本发明中使用的聚碳酸酯：
组分a-1：PC苯酚类物质含量为8ppm，制备方法：在液相苯酚类物质中加入定量的NaOH水溶液进行界面聚合，得到中间产物DPC，然后通过洗涤控制苯酚类物质残余量为8ppm和双酚A通过熔融酯交换反应得到最终产品。
组分a-2：PC苯酚类物质含量为18ppm，制备方法：在液相苯酚类物质中加入定量的NaOH水溶液进行界面聚合，得到中间产物DPC，然后通过洗涤控制苯酚类物质残余量为18ppm和双酚A通过熔融酯交换反应得到最终产品。
组分a-3：PC苯酚类物质含量为60ppm，制备方法：在液相苯酚类物质中加入定量的NaOH水溶液进行界面聚合，得到中间产物DPC，然后通过洗涤控制苯酚类物质残余量为60ppm和双酚A通过熔融酯交换反应得到最终产品。
其中所使用的苯酚类物质：
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ABS树脂：
组分b-1：ABS 8391(上海高桥)
组分b-2：ABS 757(台湾奇美)
本发明中使用的阻燃剂：
组分c-1：BDP(双酚A-双(磷酸三苯酯)，艾迪科；
组分c-2：RDP(间苯二酚-双(磷酸二苯酯)，浙江万盛；
组分c-3：TPP(磷酸三苯酯)，天津超越；
本发明中使用的其它助剂：
组分d-1：AO168：三[2.4-二叔丁基苯基]亚磷酸酯作为稳定剂；(BASF)
组分d-2：PETS：作为润滑剂(美国龙沙)
组分d-3：PTFE：聚四氟乙烯作为抗滴落剂(广州熵能)。
实施例1-9及对比例1-11：聚碳酸酯组合物的制备
将含锰化合物以及含锌化合物与苯基硅氧烷配成质量分数为0.15ppm-300ppm的苯基硅氧烷溶液；将该苯基硅氧烷溶液与含有8ppm-60ppm 苯酚类物质的聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；将预处理的聚碳酸酯、接枝共聚物、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；对聚碳酸酯组合物的粘度比(100h、150h)和冲击性能保持率(150h)进行测试，数据见表1。
表1 实施例1-9及对比例1-11的具体配比(重量份)及其测试性能结果
Figure PCTCN2016083624-appb-000002
续表1
Figure PCTCN2016083624-appb-000003
从表1的实施例和对比例的比较可以看出：选用聚碳酸酯组合物配方中的苯酚类物质基于聚碳酸酯组合物的总重量中不超过20ppm，以及金属锌元素与锰元素的复配总量基于聚碳酸酯组合物的总重量中不超过200ppm时，得到的聚碳酸酯组合物具有优异的高温高湿性能稳定性和机械性能。

Claims (13)

  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份的聚碳酸酯；
    b、8份-50份的ABS树脂；
    c、2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、44份-75份的聚碳酸酯；
    b、8份-30份的ABS树脂；
    c、5份-18份的阻燃剂；
    d、0.1-8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大于等于1ppm和小于等于20ppm；
    基于聚碳酸酯组合物的总重量中金属锌元素与锰元素的复配总量不超过200ppm；
    其中苯酚类物质的结构式如式(1)：
    Figure PCTCN2016083624-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。
  3. 根据权利要求2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10ppm和大于等于2ppm；优选为小于等于8ppm和大于等于3ppm。
  4. 根据权利要求2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金属锌元素与锰元素的复配总量不超过100ppm，优选不超过50ppm。
  5. 根据权利要求2或4任一项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金属锌元素与锰元素的复配重量比为0.2-20；优选为1-10；更优选为1.5-5。
  6. 根据权利要求1或2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。
  7. 根据权利要求6所述的聚碳酸酯组合物，其特征在于，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或2所述的聚碳酸酯组合物，其特征在于，所述ABS树脂选自本体聚合法、本体-悬浮聚合法、乳液聚合法制备的ABS树脂的一种或几种；其中，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。
  9. 根据权利要求1或2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、含氮和磷的阻燃剂中的一种或几种，优选为含磷阻燃剂。
  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。
  11. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述其它助剂选自增韧剂，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。
  12. 一种如权利要求1-11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)将含锰化合物以及含锌化合物与苯基硅氧烷配成质量分数为0.15ppm-300ppm的苯基硅氧烷溶液；
    2)将该苯基硅氧烷溶液与含有8ppm-60ppm苯酚类物质的聚碳酸酯在高混机中进行共混，得到预处理的聚碳酸酯；
    3)将预处理的聚碳酸酯、接枝共聚物、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。
  13. 根据权利要求12所述的聚碳酸酯组合物的制备方法，其特征在于，所述含锰化合物选自二氧化锰、氯化锰、硝酸锰、碳酸锰、硫酸锰中的一种或几种；所述含锌化合物选自氯化锌、硫酸锌、硝酸锌、碳酸锌、硫化锌中的一种或几种。
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