WO2018095190A1 - 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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WO2018095190A1
WO2018095190A1 PCT/CN2017/107747 CN2017107747W WO2018095190A1 WO 2018095190 A1 WO2018095190 A1 WO 2018095190A1 CN 2017107747 W CN2017107747 W CN 2017107747W WO 2018095190 A1 WO2018095190 A1 WO 2018095190A1
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polycarbonate
polycarbonate composition
potassium
flame retardant
parts
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PCT/CN2017/107747
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English (en)
French (fr)
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岑茵
田征宇
李明昆
何继辉
佟伟
丁超
谢湘
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金发科技股份有限公司
上海金发科技发展有限公司
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Publication of WO2018095190A1 publication Critical patent/WO2018095190A1/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
    • 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
    • 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

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 Hot oxygen aging performance and weathering performance hazards, especially when the use environment is relatively high, the surface is easy to form defects and its color is easy to change.
  • Patent CN102292393 discloses that the use of salt inclusions can improve the surface quality after hot wet storage and is therefore suitable for the preparation of molded articles having an ageing resistant defect-free A-grade surface;
  • the potassium element in the polycarbonate composition is added by adding a potassium-containing compound having a lower soluble potassium content and reducing or avoiding the addition of other potassium-containing compounds.
  • the content is controlled in the range of 1-40 ppm, and the obtained polycarbonate composition can be baked at 90 ° C and 90% humidity for 500 h, the moisture heat aging resistance retention rate is more than 70%, and baked at 85 ° C for 200 h.
  • the color difference value after the color difference is less than 8, and the color level is 3 or more, which not only has a markedly improved heat aging resistance but also has excellent color stability.
  • 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 components:
  • the potassium element has a weight content of 10 ppm to 200 ppm based on the total weight of the polycarbonate composition.
  • the weight content of the potassium element is determined by the following method: weigh 200 mg of the polycarbonate composition sample (accurate to 0.1 mg) into a 50 ml volumetric flask, add 5 ml of nitric acid, 0.1-1 ml of hydrogen peroxide, and bring the water to a designated scale. Cap the lid and put it into the microwave to dissolve. Open the cap, cool to room temperature, add 4ml of HCL solution, cover the cap, put it into the microwave for secondary digestion, then cool to room temperature, filter, and take 1ml of the digestion solution through Agilent Tcechnologies 700series was tested by ICP-MS mixing method, and finally the potassium content in the polycarbonate composition was measured, and the detection limit was 2 ppm.
  • the present inventors have found that by adding a potassium-containing compound having a lower soluble potassium content in a polycarbonate composition, and reducing or avoiding the addition of other potassium-containing compounds, and controlling the content of potassium element in the polycarbonate composition.
  • the hydrolytic stability of the polycarbonate resin in a hot and humid environment can be stabilized, and the obtained polycarbonate composition can be baked at 90 ° C and 90% humidity for 500 h, and the heat and humidity aging resistance is maintained.
  • the rate is more than 70%
  • the color difference after baking at 85 ° C for 200 hours is less than 8
  • the color grade is 3 or above
  • the moisture heat aging resistance can be obviously improved
  • the color stability is excellent.
  • the content of potassium element is higher than 200 ppm, the composition has a problem of appearance hazard in the injection molding process, and when the content of potassium element is less than 10 ppm, the rate of decay of moist heat aging increases.
  • the potassium element has a weight content of from 30 ppm to 150 ppm, more preferably from 50 ppm to 100 ppm, based on the total weight of the polycarbonate composition.
  • the potassium element is derived from a potassium-containing compound
  • the potassium-containing compound is selected from the group consisting of a non-halogenated +1 valent soluble potassium salt, specifically selected from one or more of potassium sulfate, potassium phosphate, potassium nitrate, and potassium sulfonate.
  • the potassium-containing compound is preferably added in an amount such that the content of the potassium element in the polycarbonate composition is in the range of 10 ppm to 200 ppm.
  • 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; It is preferably an aromatic polycarbonate.
  • the polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, more preferably an aromatic polycarbonate having a viscosity average molecular weight of 16,000 to 28,000.
  • the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained.
  • the viscosity average molecular weight was tested by a viscosity method using 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 graft copolymer is selected from the group consisting of a bulk polymerization method, an emulsion polymerization method, and a bulk-suspension polymerization method.
  • a bulk polymerization method an emulsion polymerization method
  • a bulk-suspension polymerization method One or more of the graft copolymers prepared.
  • 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.
  • the prepolymerization is carried out in a prepolymerization kettle.
  • 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 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 graft copolymer is selected from the group consisting of acrylonitrile-styrene copolymer AS, acrylonitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-acrylonitrile-butadiene styrene copolymer MABS, One or more of acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene graft copolymer MBS; wherein the particle size of MBS is preferably 0.1 um-0.5 um,
  • the bulk polymerization method ABS particle size is preferably 0.1 um to 2 um
  • the emulsion polymerization method ABS particle diameter is preferably 0.05 um to 0.2 um.
  • ABS acrylonitrile-butadiene-styrene graft copolymer ABS in which the butadiene rubber polymer has a weight fraction of 5 wt% to 50 wt% in ABS, and the particle size distribution may be uniform or have two Or multiple distributions of the above peaks.
  • 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 mineral filler may specifically be talc, wollastonite, kaolin, clay, whiskers, diatomaceous earth, etc., the mineral filler may be without any surface treatment, or may be coated, such as an alkyl group. Surface coating, epoxy surface treatment, amide surface treatment, hydroxy silicone oil, alkyl silane, methoxy silane, sulfonic acid group, etc.
  • the polycarbonate composition of the present invention may further comprise 0-20 parts by weight of other auxiliaries, such as selected from the group consisting of stabilizers, anti-drip agents, lubricants, mold release agents, plasticizers, One or several of the colorants.
  • auxiliaries such as selected from the group consisting of stabilizers, anti-drip agents, lubricants, mold release agents, plasticizers, One or several of the colorants.
  • Suitable stabilizers include organic phosphites such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-decylphenyl phosphite, dimethylphenylphosphonic acid Ester, trimethyl phosphate, etc., pentaerythritol diphosphate (such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate), organic phosphite, alkylated monohydric phenol or Polyphenols, alkylation products of polyphenols and dienes, butylated reaction products of p-cresol or dicyclopentadiene, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, One or more combinations of alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones.
  • organic phosphites
  • Suitable anti-drip agents are preferably fluorinated polyolefins such as polytetrafluoroethylene.
  • a suitable plasticizer is a phthalate.
  • the lubricant is one or a mixture of two or more of ethylene bisstearamide EBS, erucamide, silicone oil, PETS.
  • Suitable release agents include metal stearates, alkyl stearates, pentaerythritol stearate, paraffin, montan wax, and the like.
  • Suitable colorants include various pigments, dyes such as carbon black and the like.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the pretreated polycarbonate, graft copolymer, flame retardant, mineral filler, and other auxiliary agents are weighed according to the ratio, and then blended, extruded, and cooled by a high-mixer or a mixer.
  • the granules give a polycarbonate composition of columnar granules.
  • the invention has the following beneficial effects:
  • the present invention can control the content of potassium element in the polycarbonate composition in the range of 10-200 ppm in the polycarbonate composition by adding a potassium-containing compound having a lower soluble potassium content and reducing or avoiding the addition of other potassium-containing compounds.
  • the moisture heat aging resistance retention rate is more than 70%, which significantly improves the thermo-oxygen stability of the polycarbonate composition
  • the color difference is less than 8, and the color grade is 3 or above, which has excellent color stability.
  • PC has a molecular weight of 24,000 (Mitsubishi, Japan);
  • the graft copolymer used in the present invention is graft copolymer used in the present invention:
  • ABS emulsion polymerization method particle size 0.05um-0.2um, wherein the butadiene rubber polymer weight fraction in ABS is 25wt%, 757 (Taiwan Chi Mei);
  • BDP bisphenol A-bis(diphenyl phosphate) CR741 (Japan Big Eight);
  • potassium-containing compounds used in the present invention such as potassium sulfate and potassium phosphate, are all commercially available;
  • PEP-36 bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphate
  • Anti-drip agent PTFE (polytetrafluoroethylene) micro powder, Daikin
  • Colorant carbon black M717, Cabot.
  • Test method for potassium content Weigh 200mg of polycarbonate composition sample (accurate to 0.1mg) into 50ml volumetric flask, add 5ml nitric acid, 0.1-1ml hydrogen peroxide, add water to the specified scale, cover the cap Dissolve in a microwave oven, open the cap, cool to room temperature, add 4ml of HCL solution, cover the cap, put it into the microwave for secondary digestion, then cool to room temperature, filter, take 1ml of digestion solution through ICP-MS of Agilent Tcechnologies 700series The mixed standard method was tested, and finally the potassium content in the composition was measured, and the detection limit was 2 ppm.
  • Moisture and heat aging resistance The extruded pellets are molded into ASTM standard tensile type I test panels at 270 ° C injection temperature. After injection molding, they are placed in a constant temperature and humidity environment at 25 ° C and 25% humidity for 48 h. The plate was placed in a constant temperature oven placed at 90 ° C and 90% humidity for 500 hours, and then taken out at a temperature of 25 ° C and a constant humidity of 25% humidity for 48 hours. The tensile strength before and after the placement was recorded (test speed was 10 mm). /min), the performance retention rate is calculated by calculation;
  • the potassium-containing compound is formulated into a 0.01% by mass aqueous solution of distilled water; the solution is quantitatively added to a high-mixer containing a polycarbonate resin at a premixing temperature of 70 ° C to 80 ° C by a liquid pump, and the blending time is After 2min-5min, the temperature is raised to 110°C-120°C for 20min-30min to obtain pretreated polycarbonate; the pretreated polycarbonate, graft copolymer, flame retardant, according to the formulation of Table 1 Mineral fillers and other auxiliaries are weighed in proportion, and then blended by high-mixer or mixer, extruded, cooled by water, granulated to obtain columnar granules of polycarbonate composition; performance of polycarbonate composition Test, the data is shown in Table 1.
  • the content of potassium element in the polycarbonate composition is controlled to 10 by adding a potassium-containing compound having a lower soluble potassium content to the polycarbonate composition.
  • the obtained polycarbonate composition can be baked at 90 ° C and 90% humidity for 500 h, and the moisture heat aging resistance retention rate is more than 70%, which significantly improves the heat and moisture aging resistance of the polycarbonate composition.
  • the color difference is less than 8, and the color grade is 3 or above, which has excellent color stability.
  • Comparative Example 1-2 when the content of the potassium element in the polycarbonate composition was less than 10 ppm or more than 200 ppm, the polycarbonate composition was inferior in moist heat aging resistance and color stability.

Abstract

本发明公开了一种聚碳酸酯组合物及其制备方法，按重量份计，包括以下组份： 30份-75份的聚碳酸酯； 0份-35份的接枝共聚物； 5份-25份的阻燃剂； 5份-35份的矿物填料；其中，基于聚碳酸酯组合物的总重量，钾元素的重量含量为10ppm-200ppm。本发明通过在聚碳酸酯组合物中添加具有较低可溶性钾含量的含钾化合物以及减少或者避免其它含钾化合物的加入，将聚碳酸酯组合物中钾元素的含量控制在10-200ppm范围内，可以使制得的聚碳酸酯组合物在90℃和90％湿度下烘烤500h后，耐湿热老化性能保持率大于70％，具有明显改善的耐湿热老化性能，且在85℃烘烤200h后的色差值小于8，颜色等级3级或以上，具有优良的颜色稳定性。

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，其表面容易形成缺陷以及其颜色容易发生变化。
专利CN102292393公开了使用盐夹杂物能改善在热湿储存之后的表面质量，因此适合于制备具有耐老化的无缺陷A级表面的模塑品；
本发明人经过大量实验惊讶地发现，在聚碳酸酯组合物中，通过添加具有较低可溶性钾含量的含钾化合物以及减少或者避免其它含钾化合物的加入，将聚碳酸酯组合物中钾元素的含量控制在1-40ppm范围内，可以使制得的聚碳酸酯组合物在90℃和90％湿度下烘烤500h后，耐湿热老化性能保持率大于70％，且在85℃烘烤200h后的色差值小于8，颜色等级3级或以上，不仅具有明显改善的耐湿热老化性能，而且具有优良的颜色稳定性。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种具有明显改善耐湿热老化性能和优良的颜色稳定性的聚碳酸酯组合物。
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，包括以下组份：
30份-75份的聚碳酸酯；
0份-35份的接枝共聚物；
5份-25份的阻燃剂；
5份-35份的矿物填料；
其中，基于聚碳酸酯组合物的总重量，钾元素的重量含量为10ppm-200ppm。
所述钾元素的重量含量采用如下方法测定：称取200mg聚碳酸酯组合物样品(精确到0.1mg)到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解，打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700series的ICP-MS混标法进行测试，最后测出聚碳酸酯组合物中的钾元素含量，检出限为2ppm。
本发明经过研究发现，在聚碳酸酯组合物中通过添加具有较低可溶性钾含量的含钾化合物，以及减少或者避免其它含钾化合物的加入，并将聚碳酸酯组合物中钾元素的含量控制在10ppm-200ppm范围内，可稳定聚碳酸酯树脂在湿热环境中的水解稳定性，可以使制得的聚碳酸酯组合物在90℃和90％湿度下烘烤500h后，耐湿热老化性能保持率大于70％，在85℃烘烤200h后的色差值小于8，颜色等级3级或以上，可明显改善的耐湿热老化性能，且具有优良颜色稳定性。当钾元素的含量高于200ppm时，组合物存在注塑过程中的外观隐患问题，当钾元素的含量低于10ppm时，湿热老化衰减速率增加。
优选的，基于聚碳酸酯组合物的总重量，钾元素的重量含量为30ppm-150ppm，更优选为50ppm-100ppm。
其中，所述钾元素来源于含钾化合物，含钾化合物选自非卤系的+1价可溶性钾盐，具体选自硫酸钾、磷酸钾、硝酸钾、磺酸钾中的一种或几种。含钾化合物的添加量以使聚碳酸酯组合物中钾元素的含量为10ppm-200ppm范围内为宜。
其中，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。
所述聚碳酸酯为粘均分子量13000-40000的芳香族聚碳酸酯，更优选为粘均分子量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，粘均分子量通过粘度法测试：以二氯甲烷作为溶剂，测试温度为25℃。
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，所述接枝共聚物选自本体聚合法、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。
所述接枝共聚物选自丙烯腈-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；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。
进一步优选为丙烯腈-丁二烯-苯乙烯接枝共聚物ABS，其中丁二烯橡胶质聚合物在ABS中的重量分数为5wt％-50wt％，粒径分布可以是均匀的或者具有两个或者以上峰值的多分布。
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。
所述矿物填料，具体可以为滑石粉、硅灰石、高岭土、黏土、晶须、硅藻土等等，矿物填料可以是不进行任何表面处理的，也可以是涂覆处理的，例如烷基表面包覆，环氧表面处理，酰胺表面处理，羟基硅油，烷基硅烷，甲氧基硅烷，磺酸基等处理。
根据不同的用途需要，本发明的聚碳酸酯组合物中还可以包含0-20重量份的其它助剂，如选自稳定剂、抗滴落剂、润滑剂、脱模剂、增塑剂、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，季戊四醇双磷酸酯(如双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)，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。
合适的抗滴落剂为优选为氟化聚烯烃，如聚四氟乙烯。
合适的增塑剂为邻苯二甲酸酯。
所述润滑剂为乙撑双硬脂酰胺EBS、芥酸酰胺、硅油、PETS中的一种或者两种及以上的混合物。
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，如炭黑等。
上述聚碳酸酯组合物的制备方法，包括如下步骤：
1)将含钾化合物配成0.01％质量分数的蒸馏水溶液；
2)将溶液通过液体泵定量加入到预混温度为70℃-80℃的含有聚碳酸酯树脂的高混机中进行共混，共混时间为2min-5min，后将温度升高到110℃-120℃维 持20min-30min，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、矿物填料、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。
本发明与现有技术相比，具有如下有益效果：
本发明在聚碳酸酯组合物中，通过添加具有较低可溶性钾含量的含钾化合物以及减少或者避免其它含钾化合物的加入，将聚碳酸酯组合物中钾元素的含量控制在10-200ppm范围内，可以使制得的聚碳酸酯组合物在90℃和90％湿度下烘烤500h后，耐湿热老化性能保持率大于70％，明显改善了聚碳酸酯组合物的热氧稳定性，且在85℃烘烤200h后的色差值小于8，颜色等级3级或以上，具有优良的颜色稳定性。
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。
本发明中使用的聚碳酸酯：
PC 粘分子量为24000(日本三菱)；
本发明中使用的接枝共聚物：
ABS 乳液聚合法，粒径0.05um-0.2um，其中丁二烯橡胶质聚合物在ABS中的重量分数为25wt％，757(台湾奇美)；
MBS 粒径0.1um-0.5um，EM500(韩国LG)；
本发明中使用的阻燃剂：
BDP，双酚A-双(磷酸二苯基酯)CR741(日本大八)；
矿物填料：滑石粉H30(林化成)；
本发明中使用的含钾化合物如硫酸钾、磷酸钾均来源于市购；
本发明中使用的其它助剂：
稳定剂：PEP-36(双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯)；
润滑剂：PETS，龙沙；
抗滴落剂：PTFE(聚四氟乙烯)微粉，大金
着色剂：炭黑M717，卡博特。
各性能的测试标准或方法：
钾元素含量的测试方法：称取200mg聚碳酸酯组合物样品(精确到0.1mg)到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解，打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700series的ICP-MS混标法进行测试，最后测出组合物中的钾元素含量，检出限为2ppm。
耐湿热老化性能：将挤出的粒子在270℃注塑温度下成型为ASTM标准拉伸I型的测试板材，注塑后放置在25℃温度以及25％湿度的恒温恒湿环境下48h后，将测试板放于放于90℃和90％湿度的恒温烘箱烘烤500h后取出，放置在25℃温度以及25％湿度的恒温恒湿环境下48h后，记录放置前后的拉伸强度(测试速度为10mm/min)，通过计算得出性能保持率；
颜色稳定性：将挤出的粒子在270℃注塑温度下成型为100mm*100mm*2mm的测试板材，注塑后放置在25℃温度以及25％湿度的恒温恒湿环境下48h后，记录YI值为YI0，后将测试板放于85℃恒温烘箱烘烤200h后取出，放置在25℃温度以及25％湿度的恒温恒湿环境下48h后，记录YI值为YI，通过公式YI-YI0计算等级，计算值<3为等级1，3<计算值<5为等级2；5<计算值<8为等级3；计算值>8为等级4；
实施例1-16及对比例1-2：聚碳酸酯组合物的制备
将含钾化合物配成0.01％质量分数的蒸馏水溶液；将溶液通过液体泵定量加入到预混温度为70℃-80℃的含有聚碳酸酯树脂的高混机中进行共混，共混时间为2min-5min，后将温度升高到110℃-120℃维持20min-30min，得到预处理的聚碳酸酯；按表1的配方将预处理的聚碳酸酯、接枝共聚物、阻燃剂、矿物填料、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；对聚碳酸酯组合物进行性能测试，数据见表1。
表1 实施例1-16及对比例1-2的具体配比(重量份)及其测试性能结果
Figure PCTCN2017107747-appb-000001
续表1：
Figure PCTCN2017107747-appb-000002
Figure PCTCN2017107747-appb-000003
从表1的实施例和对比例的比较可以看出：通过在聚碳酸酯组合物中添加具有较低可溶性钾含量的含钾化合物，将聚碳酸酯组合物中钾元素的含量控制在10-200ppm范围内，可以使制得的聚碳酸酯组合物在90℃和90％湿度下烘烤500h后，耐湿热老化性能保持率大于70％，明显改善了聚碳酸酯组合物的耐湿热老化性能，且在85℃烘烤200h后的色差值小于8，颜色等级3级或以上，具有优良的颜色稳定性。对比例1-2中，聚碳酸酯组合物中钾元素的含量低于10ppm或高于200ppm时，聚碳酸酯组合物的耐湿热老化性能和颜色稳定性均较差。

Claims (12)

  1. 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组份：
    30份-75份的聚碳酸酯；
    0份-35份的接枝共聚物；
    5份-25份的阻燃剂；
    5份-35份的矿物填料。
  2. 根据权利要求1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，钾元素的重量含量为10ppm-200ppm。
  3. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述钾元素的重量含量采用如下方法测定：称取200mg聚碳酸酯组合物样品,精确到0.1mg,到50ml容量瓶中，加入5ml硝酸，0.1-1ml过氧化氢，加水定容到指定刻度，盖上瓶盖放入微波炉消解,打开瓶盖，冷却到室温，加入4mlHCL液，盖上瓶盖，放入微波炉中二次消解，后冷却到室温，过滤，将消解液取1ml通过Agilent Tcechnologies 700 series的ICP-MS混标法进行测试，最后测出聚碳酸酯组合物中的钾元素含量，检出限为2ppm。
  4. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，基于聚碳酸酯复合材料的总重量，钾元素的重量含量为30ppm-150ppm，优选为50ppm-100ppm。
  5. 根据权利要求1-4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。
  6. 根据权利要求5所述的聚碳酸酯组合物，其特征在于，所述芳香族聚碳酸酯选自粘均分子量13000-40000的芳香族聚碳酸酯，粘均分子量通过粘度法测试：以二氯甲烷作为溶剂，测试温度为25℃，优选为粘均分子量16000-28000的芳香族聚碳酸酯。
  7. 根据权利要求1-4任一项所述的聚碳酸酯组合物，其特征在于，所述接枝共聚物选自丙烯腈-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。
  8. 根据权利要求1-4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、含氮和磷的阻燃 剂中的一种或几种，优选为含磷阻燃剂。
  9. 根据权利要求8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。
  10. 根据权利要求1-4任一项所述的聚碳酸酯组合物，其特征在于，所述钾元素来源于含钾化合物，所述含钾化合物选自非卤系的+1价可溶性钾盐，具体选自硫酸钾、磷酸钾、硝酸钾、磺酸钾中的一种或几种。
  11. 根据权利要求1-4任一项所述的聚碳酸酯组合物，其特征在于，所述聚碳酸酯组合物还包括0-20重量份其它助剂，所述其它助剂选自稳定剂、抗滴落剂、润滑剂、脱模剂、增塑剂、着色剂的一种或几种。
  12. 根据权利要求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)将含钾化合物配成0.01％质量分数的蒸馏水溶液；
    2)将溶液通过液体泵定量加入到预混温度为70℃-80℃的含有聚碳酸酯树脂的高混机中进行共混，共混时间为2min-5min，后将温度升高到110℃-120℃维持20min-30min，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、矿物填料、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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