WO2016202160A1 - 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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WO2016202160A1
WO2016202160A1 PCT/CN2016/083635 CN2016083635W WO2016202160A1 WO 2016202160 A1 WO2016202160 A1 WO 2016202160A1 CN 2016083635 W CN2016083635 W CN 2016083635W WO 2016202160 A1 WO2016202160 A1 WO 2016202160A1
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parts
phosphate
polycarbonate
containing prepolymer
terpolymer
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PCT/CN2016/083635
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English (en)
French (fr)
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岑茵
孙东海
何继辉
佟伟
谢湘
谢修好
田征宇
郭唐华
董相茂
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金发科技股份有限公司
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Priority to EP16810901.5A priority Critical patent/EP3312239B1/en
Publication of WO2016202160A1 publication Critical patent/WO2016202160A1/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
    • 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
    • C08L51/04—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 rubbers
    • 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
    • C08L2201/08—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
  • polycarbonate PC has high oxygen index and has certain fire resistance. It can reach UL94 flame retardant grade V-2 and is widely used.
  • V-2 flame retardant grade
  • the demand for miniaturization and weight reduction, thinning, and non-halogenation has become more and more urgent.
  • flame retardant requirements for polycarbonate composition materials have been met. It is getting higher and higher, especially the requirement that the flame retardant grade of thin products reach V-0, and the shorter the burning time, the better, and the smaller the amount of smoke, the better.
  • the inventors have surprisingly found through extensive experimentation that it is possible to significantly improve the heat resistance of the polycarbonate composition by adding a specific content of the phosphorus-containing prepolymer and the fluorine-containing prepolymer in the polycarbonate composition formulation.
  • the polycarbonate composition is capable of maintaining good mechanical properties as well as appearance.
  • 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 five components a, b, c, d, and e is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the five components a, b, c, d, and e is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the five components a, b, c, d, and e is 100 parts.
  • the test method for the phosphorus-containing prepolymer is as follows: after the composition particles are subjected to sonic extraction for 48 hours at a temperature of 85 ° C, the extract particles are taken out, and 2 uL of the extract is taken out, and the styrene is introduced at a constant flow rate at normal temperature.
  • the adsorption-type column, the total phosphorus-containing prepolymer content in the system is calculated according to the integral area ratio of the outflow time and the total outflow time;
  • the fluorine-containing prepolymer is tested by placing the composition particles in a Ar/O 2 gas stream at 900 ° C for combustion treatment, and generating a gas absorption liquid for absorption by ion chromatography (IC method).
  • IC method ion chromatography
  • the content of the phosphorus-containing prepolymer exceeds 10 parts, it is not easy to form a uniform dispersion in the system, and the amount of smoke is not suppressed, but the rate of smoke release is accelerated, the amount of smoke is increased, and the surface appearance problem is more likely to occur. .
  • the modified composition may cause retention fluidity due to severe fiber formation, resulting in difficulty in processing, and it is impossible to smoothly form complicated parts and thin-walled parts, and is thermally stable. Sex will also decrease.
  • the fluorine-containing prepolymer is one or more selected from the group consisting of a polymer of fluorinated ethylene, difluoroethylene, tetrafluoroethylene, hexafluoroethylene, vinylidene fluoride, and a copolymer of tetrafluoroethylene and hexafluoroethylene.
  • it is tetrafluoroethylene; wherein the fluorine-containing prepolymer has a degree of polymerization of 500,000 or less and 100,000 or more.
  • 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; Preferred is an aromatic polycarbonate;
  • the aromatic polycarbonate is an aromatic polycarbonate having a viscosity average molecular weight of 13,000 to 40,000, 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 terpolymer is selected from one or more of terpolymers prepared by bulk polymerization, emulsion polymerization, bulk-suspension polymerization.
  • 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.
  • terpolymer in parts by weight, is selected from the group consisting of graft copolymers of b.1 and b.2 as follows:
  • 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 terpolymer is selected from the group consisting of acrylonitrile-styrene copolymer AS, acrylonitrile-butadiene-styrene terpolymer ABS, methyl methacrylate-acrylonitrile-butadiene styrene copolymerization
  • MABS acrylonitrile-styrene-acrylic acid terpolymer ASA, methyl methacrylate-butadiene-styrene terpolymer MBS; preferably acrylonitrile-butadiene- Styrene terpolymer ABS and/or methyl methacrylate-butadiene-styrene terpolymer MBS; wherein the particle size of MBS is preferably from 0.1 um to 0.5 um, and the bulk polymerization method ABS particle size is preferably 0.1.
  • Um-2um, emulsion polymerization ABS particle size is preferably 0.05um-0.2um.
  • the phosphate 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), P-phenylene Phenol bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol bis(2,6-di-tert-butylphenyl phosphate), hydroquinone bis (2) One or more of 6-dimethylphenyl phosphate.
  • the polycarbonate composition may further comprise other auxiliary agents; the other auxiliary agent is selected from one or more of a stabilizer, an antioxidant, a flame retardant synergist, a lubricant, a plasticizer, 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
  • Suitable antioxidants include phenolic antioxidants, and more specifically 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate, tetrakis(methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane, tris(3,5-di-tert-butyl) 4-hydroxybenzyl)isocyanate, 4,4-butylbis-(3-methyl-6-tert-butylphenol), triethylene glycol-bis(3-(3-tert-butyl-hydroxy-5-) Methylbenzyl)propionate and 3.9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxyl-1,1-dimethylphenyl) -2,4,8,10-tetraoxaspiro(5,
  • Suitable flame retardant synergists include inorganic fillers such as metal oxides, carbonates, phosphates, silicates, sulfides, silicon-containing materials, such as titanium dioxide, talc, hydrotalcite, barium sulfate, calcium carbonate, Zinc sulphide, wollastonite and silicone, silicone.
  • inorganic fillers such as metal oxides, carbonates, phosphates, silicates, sulfides, silicon-containing materials, such as titanium dioxide, talc, hydrotalcite, barium sulfate, calcium carbonate, Zinc sulphide, wollastonite and silicone, silicone.
  • Suitable lubricants include aliphatic monocarboxylic acids, dicarboxylic acids or tricarboxylic acids, such as palmitic acid, stearic acid, valeric acid, caproic acid, sunflower acid, dodecyl acid, eicosyl acid, Dodecyl acid, tetracosyl acid, dihexadecyl acid, tridecyl acid, tridecyl acid, montanic acid, glutaric acid, adipic acid and sebacic acid.
  • aliphatic monocarboxylic acids such as palmitic acid, stearic acid, valeric acid, caproic acid, sunflower acid, dodecyl acid, eicosyl acid, Dodecyl acid, tetracosyl acid, dihexadecyl acid, tridecyl acid, tridecyl acid, montanic acid, glutaric acid, adipic acid and sebacic acid.
  • a suitable plasticizer is a phthalate.
  • Suitable fillers include various columnar, spherical, acicular, and irregular materials such as glass, carbon fibers, cotton fibers, metals, metal compounds, and the like.
  • Suitable colorants include various pigments, dyes.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the polycarbonate, the terpolymer, the phosphate flame retardant, the phosphorus-containing prepolymer, the fluorine-containing prepolymer, and other auxiliary agents are weighed in proportion, and then blended and extruded through a high-mixer or a mixer. , water cooling, granulation A polycarbonate composition of columnar particles is obtained.
  • the invention has the following beneficial effects:
  • the present invention can significantly improve the heat resistance of the polycarbonate composition by selecting a specific content of the phosphorus-containing prepolymer and the fluorine-containing prepolymer in the polycarbonate composition formulation, while the polycarbonate composition can maintain Very good mechanical properties and appearance.
  • Test method for heat resistance Using a 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd., the polycarbonate composition was retained at a cylinder temperature of 280 ° C for 5 minutes, and the viscosity average molecular weight before and after the injection was measured to evaluate the stability of the composition. Sex. The smaller the absolute value of the difference between the "viscosity average molecular weight after injection” and the “viscosity average molecular weight before injection”, the more preferable.
  • the evaluation is "good (G)”
  • M medium
  • the absolute value of the difference is 10000 or more.
  • the evaluation is "bad (NG)”.
  • 2.0mm flame retardant test method UL94: injection into 1.5mm thickness, 125mm length and 13mm width strip spline, according to vertical burning flame time and drip ignition phenomenon evaluation method to determine V-0, V-1, V-2 level;
  • Test method for the amount of smoke Using an 80-ton injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a 4 mm*100 mm*100 mm sample with a uniform shape and uniform material is burned at a barrel temperature of 280 ° C, and burned in the balance. After the burning RSR data curve is processed, the dynamic combustion behavior is comprehensively evaluated by the smoke generation rate SPR, the total smoke generation TSP, the smoke parameter SP, and the smoke factor SF, and the evaluation means that the result is large, medium, and small.
  • Test method for appearance Using an 80-ton injection molding machine manufactured by Nissei Resin Co., Ltd., the sample was held at a temperature of 280 ° C for 5 minutes, and a sample of 2 mm * 100 mm * 100 mm was injected, and the composition was evaluated by observing the surface condition of the sample. stability. Here, there is no water and silver plaque, which is evaluated as “good (G)”, with slight pitting or length less than 1mm, and the evaluation is “medium (M)”, serious sacks and more, and the length is more than 1mm. The evaluation is "bad (NG)”.
  • the test method for the phosphorus-containing prepolymer is as follows: after the composition particles are subjected to sonic extraction for 48 hours at a temperature of 85 ° C, the extract particles are taken out, and 2 uL of the extract is taken out, and the styrene is introduced at a constant flow rate at normal temperature. Absorption column, based on the ratio of the outflow time to the total area of the total outflow time to calculate the total phosphorus in the system The content of the polymer;
  • the fluorine-containing prepolymer is tested by placing the composition particles in a Ar/O 2 gas stream at 900 ° C for combustion treatment, and generating a gas absorption liquid for absorption by ion chromatography (IC method).
  • IC method ion chromatography
  • Component a-1 PC 1300-10 (LG, Korea);
  • Component a-2 PC 1225 (Japanese Teijin);
  • Component b-1 ABS1 emulsion method 757 (Taiwan Chi Mei);
  • Component b-2 MBS EM500 (LG LG, Korea);
  • Phosphate flame retardant used in the present invention is Phosphate flame retardant used in the present invention:
  • Component c BDP, bisphenol A-bis(diphenyl phosphate) (Idico);
  • Phosphorus-containing prepolymers for use in the present invention are Phosphorus-containing prepolymers for use in the present invention:
  • Component d-1 bisphenol A-bis(diphenyl phosphate) dimer (Idico);
  • Component d-2 bisphenol A-bis(diphenyl phosphate) trimer (Idico);
  • Component e-1 tetrafluoroethylene prepolymer having a degree of polymerization of 200,000 (3M in the United States);
  • Component e-2 a vinylidene fluoride prepolymer having a degree of polymerization of 200,000 (3M in the United States);
  • Component f-1 AO1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) as an antioxidant;
  • Component f-2 pep-36 (phosphite) as a stabilizer.
  • the polycarbonate, the terpolymer, the phosphate ester flame retardant, the phosphorus-containing prepolymer, the fluorine-containing prepolymer, and other auxiliary agents are weighed according to the ratio, and then completed by a high mixer or a mixer. Blending, extruding, water cooling, granulation to obtain columnar granules of polycarbonate composition; testing of the heat resistance, flame retardancy, smoke amount and appearance of the polycarbonate composition, the data are shown in Table 1.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (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-85份的聚碳酸酯； b、8份-50份的三元共聚物； c、5份-25份的磷酸酯阻燃剂； d、0.01份-10份的含磷预聚体； e、0.01份-10份的含氟预聚体；其中，a、b、c、d、e五种组分的重量份之和为100份。本发明通过选用在聚碳酸酯组合物配方中添加特定含量的含磷预聚体和含氟预聚体，能够明显改善聚碳酸酯组合物的耐热性，同时该聚碳酸酯组合物能够保持很好的力学性能以及外观。

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，且聚碳酸酯PC的氧指数比较高，本身具有一定的防火性，可以达到UL94阻燃级别的V-2级，被广泛应用于电子电器和办公室用品以及手机等行业中，近年来，小型化和轻量化，薄壁化，无卤化的需求越来越迫切，为了满足这些需求，对聚碳酸酯组合物材料的阻燃要求越来越高，特别是要求薄制品的阻燃级别达V-0，且燃烧时间越短越好，发烟量越小越好。
目前可以通过加入阻燃剂来提高聚碳酸酯的阻燃性能，如磷酸酯类阻燃剂，但此类阻燃剂的加入会降低聚碳酸酯的耐热性能。因此在一些使用环境比较高的场合，以及加工条件苛刻的要求下，往往外观，性能，以及阻燃得不到均衡。
到目前为止，关于含磷预聚体和含氟预聚体的含量对所述聚碳酸酯组合物的耐热性及其力学性能和外观的影响未见报道。
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含磷预聚体和含氟预聚体，能够明显改善聚碳酸酯组合物的耐热性，同时该聚碳酸酯组合物能够保持很好的力学性能以及外观。
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耐热性能得到明显提高，且能保持很好的力学性能以及外观的聚碳酸酯组合物。
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-85份的聚碳酸酯；
b、8份-50份的三元共聚物；
c、5份-25份的磷酸酯阻燃剂；
d、0.01份-10份的含磷预聚体；
e、0.01份-10份的含氟预聚体；
其中，a、b、c、d、e五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、50份-75份的聚碳酸酯；
b、8份-35份的三元共聚物；
c、5份-25份的磷酸酯阻燃剂；
d、0.05份-5份的含磷预聚体；
e、0.05份-8份的含氟预聚体；
其中，a、b、c、d、e五种组分的重量份之和为100份。
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、50份-70份的聚碳酸酯；
b、8份-30份的三元共聚物；
c、5份-18份的磷酸酯阻燃剂；
d、0.1份-1份的含磷预聚体；
e、0.1份-4份的含氟预聚体；
其中，a、b、c、d、e五种组分的重量份之和为100份。
含磷预聚体的测试方法为：将组合物粒子用分析纯级别的甲醇，温度为85℃进行索式抽提48小时后，取出抽提液2uL，在常温中以一定的流速进入苯乙烯类吸附谱柱，根据流出时间与总流出时间的积分面积配比来算体系中总含磷预聚体的含量；
含氟预聚体的测试方法为：将组合物粒子放置在Ar/O 2气流中900摄氏度中燃烧处理，产生的气体吸收液吸收，使离子色谱法(IC法)比定量。
当含磷预聚体的含量超过10份，不容易在体系中形成均一的分散，发烟量不会得到抑制，反而会加速烟释放速率，发烟量增大，同时更容易导致表面外观问题。
当含氟预聚体的重量份超过10份，由于成纤严重，改性后的组合物会产生滞留流动性，导致加工困难，无法顺利成型复杂制件以及薄壁制件，同时热稳定 性也会降低。
其中，所述含磷预聚体选自分子量为200道尔顿-1000道尔顿的含有(GO)3P＝O结构的磷酸芳基酯单体的聚合物，选自十二烷基磷酸苯酯、磷酸乙基二苯酯、双酚A-双(磷酸二苯基酯)二聚体、双酚A-双(磷酸二苯基酯)三聚体、磷酸二丁基苯酯、磷酸三甲苯酯、异丙基化磷酸三苯酯磷酸对甲苯酯、异丙基化磷酸三苯酯磷酸二苯酯二聚体、异丙基化磷酸三苯酯磷酸二苯酯三聚体中的一种或几种；优选为双酚A-双(磷酸二苯基酯)二聚体、双酚A-双(磷酸二苯基酯)三聚体、磷酸三甲苯酯、异丙基化磷酸三苯酯磷酸对甲苯酯、异丙基化磷酸三苯酯磷酸二苯酯二聚体、异丙基化磷酸三苯酯磷酸二苯酯三聚体的一种或几种。
其中，所述含氟预聚体选自氟化乙烯、二氟乙烯、四氟乙烯、六氟乙烯、偏氟乙烯的聚合物、四氟乙烯与六氟乙烯的共聚物中的一种或几种；优选为四氟乙烯；其中，含氟预聚体的聚合度小于等于50万，大于等于10万。
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；
优选地，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，所述三元共聚物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的三元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，所述三元共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物：
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，所述三元共聚物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯三元共聚物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-苯乙烯三元共聚物MBS中的一种或几种；优选为丙烯腈-丁二烯-苯乙烯三元共聚物ABS和/或甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物MBS；其中，MBS的粒径优选在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。
其中，所述磷酸酯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。
该聚碳酸酯组合物还可以包括其它助剂；所述其它助剂选自稳定剂、抗氧剂、阻燃增效剂、润滑剂、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。
合适的抗氧剂包括酚类抗氧剂，并更具体的为2,6-二叔丁基-4-甲基酚，正十八烷基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯，四(亚甲基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯)甲烷，三(3,5-二叔丁基-4-羟基苄基)异氰酸酯，4,4-丁基双-(3-甲基-6-叔丁基酚)，三甘醇-双(3-(3-叔丁基-羟基-5-甲基苄基)丙酸酯和3.9-双(2-(3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧剂-1,1-二甲基苯基-2,4,8,10-四氧杂螺(5,5)十一烷等。
合适的阻燃增效剂包括无机填料如金属氧化物，碳酸盐，磷酸盐，硅酸盐，硫化物，含硅物质，具体如钛白粉，滑石粉，水滑石，硫酸钡，碳酸钙，硫化锌，硅灰石和硅氧烷，硅酮。
合适的润滑剂包括脂肪族单羧酸，二羧酸或者三羧酸，具体如棕榈酸，硬脂酸，戊酸，己酸，葵酸，十二烷基酸，二十烷基酸，二十二烷基酸，二十四烷基酸，二十六烷基酸，三十烷基酸，三十四烷基酸，褐煤酸，戊二酸，己二酸和壬二酸等。
合适的增塑剂为邻苯二甲酸酯。
合适的填料包括各种柱状的，球状的，针状的以及不规则状的如玻纤，碳纤维，棉纤维，金属，金属化合物等。
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：
将聚碳酸酯、三元共聚物、磷酸酯阻燃剂、含磷预聚体、含氟预聚体、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：
本发明通过选用在聚碳酸酯组合物配方中添加特定含量的含磷预聚体和含氟预聚体，能够明显改善聚碳酸酯组合物的耐热性，同时该聚碳酸酯组合物能够保持很好的力学性能以及外观。
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：
耐热性的测试方法：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分钟聚碳酸酯组合物，测定注射前后的粘均分子量，评价组合物的稳定性。“注射后的粘均分子量”和“注射前的粘均分子量”的差的绝对值越小越优选。这里，差的绝对值低于2000时，评价为“良好(G)”，差的绝对值为5000以上、低于10000时，评价为“中等(M)”，差的绝对值为10000以上时，评价为“不良(NG)”。
2.0mm的阻燃测试方法：UL94：注塑成1.5mm厚度，125mm长度以及13mm宽度的条状样条，根据垂直燃烧火焰时间以及滴落引燃现象的评价方法判定V-0，V-1，V-2级别；
发烟量的测试方法：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℃下注射4mm*100mm*100mm外形完整，料质均匀的样件，在天平中燃烧，对燃烧的RSR数据曲线处理后，通过生烟速度SPR，生烟总量TSP，烟参数SP，烟因子SF综合评价动态的燃烧行为，评价手段是结果为大，中，小。
外观的测试方法：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，注射2mm*100mm*100mm样件，通过观测样件表面情况，评价组合物的稳定性。这里，无任何水花银纹麻点，评价为“良好(G)”，有轻微麻点或者长度小于1mm水花银纹，评价为“中等(M)”，严重麻袋以及数量较多且长度大于1mm，评价为“不良(NG)”。
含磷预聚体的测试方法为：将组合物粒子用分析纯级别的甲醇，温度为85℃进行索式抽提48小时后，取出抽提液2uL，在常温中以一定的流速进入苯乙烯类吸附谱柱，根据流出时间与总流出时间的积分面积配比来算体系中总含磷预 聚体的含量；
含氟预聚体的测试方法为：将组合物粒子放置在Ar/O 2气流中900摄氏度中燃烧处理，产生的气体吸收液吸收，使离子色谱法(IC法)比定量。
本发明中使用的聚碳酸酯：
组分a-1：PC 1300-10(韩国LG)；
组分a-2：PC 1225(日本帝人)；
本发明中使用的三元共聚物：
组分b-1：ABS1 乳液法 757(台湾奇美)；
组分b-2：MBS EM500(韩国LG)；
本发明中使用的磷酸酯阻燃剂：
组分c：BDP，双酚A-双(磷酸二苯基酯)(艾迪科)；
本发明中使用的含磷预聚体：
组分d-1：双酚A-双(磷酸二苯基酯)二聚体(艾迪科)；
组分d-2：双酚A-双(磷酸二苯基酯)三聚体(艾迪科)；
本发明中使用的含氟预聚体：
组分e-1：四氟乙烯预聚体，聚合度为200000(美国3M)；
组分e-2：偏氟乙烯预聚体，聚合度为200000(美国3M)；
本发明中使用的其它助剂：
组分f-1：AO1076(十八烷基3-(3,5-二叔丁基-4-羟苯基)丙酸酯)作为抗氧剂；
组分f-2：pep-36(亚磷酸酯)作为稳定剂。
实施例1-15对比例1-9：聚碳酸酯组合物的制备
按表1的配方将聚碳酸酯、三元共聚物、磷酸酯阻燃剂、含磷预聚体、含氟预聚体、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耐热性、阻燃性、发烟量和外观进行测试，数据见表1。
表1实施例1-15及对比例1-9的具体配比(重量份)及其测试性能结果
Figure PCTCN2016083635-appb-000001
Figure PCTCN2016083635-appb-000002
续表1
Figure PCTCN2016083635-appb-000003
Figure PCTCN2016083635-appb-000004
从表1的实施例和对比例的比较可以看出，选用在聚碳酸酯组合物配方中添加特定含量的含磷预聚体和含氟预聚体，能够明显改善聚碳酸酯组合物的耐热性，同时该聚碳酸酯组合物能够保持很好的力学性能以及外观。

Claims (12)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、30份-85份的聚碳酸酯；
    b、8份-50份的三元共聚物；
    c、5份-25份的磷酸酯阻燃剂；
    d、0.01份-10份的含磷预聚体；
    e、0.01份-10份的含氟预聚体；
    其中，a、b、c、d、e五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、50份-75份的聚碳酸酯；
    b、8份-35份的三元共聚物；
    c、5份-25份的磷酸酯阻燃剂；
    d、0.05份-5份的含磷预聚体；
    e、0.05份-8份的含氟预聚体；
    其中，a、b、c、d、e五种组分的重量份之和为100份。
  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、50份-70份的聚碳酸酯；
    b、8份-30份的三元共聚物；
    c、5份-18份的磷酸酯阻燃剂；
    d、0.1份-1份的含磷预聚体；
    e、0.1份-4份的含氟预聚体；
    其中，a、b、c、d、e五种组分的重量份之和为100份。
  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，所述含磷预聚体选自分子量为200道尔顿-1000道尔顿的含有(GO)3P＝O结构的磷酸芳基酯单体的聚合物，选自十二烷基磷酸苯酯、磷酸乙基二苯酯、双酚A-双(磷酸二苯基酯)二聚体、双酚A-双(磷酸二苯基酯)三聚体、磷酸二丁基苯酯、磷酸三甲苯酯、异丙基化磷酸三苯酯磷酸对甲苯酯、异丙基化磷酸三苯酯磷酸二苯酯二聚体、异丙基化磷酸三苯酯磷酸二苯酯三聚体中的一种或几种；优选为双酚A-双(磷酸 二苯基酯)二聚体、双酚A-双(磷酸二苯基酯)三聚体、磷酸三甲苯酯、异丙基化磷酸三苯酯磷酸对甲苯酯、异丙基化磷酸三苯酯磷酸二苯酯二聚体、异丙基化磷酸三苯酯磷酸二苯酯三聚体的一种或几种。
  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，所述含氟预聚体选自氟化乙烯、二氟乙烯、四氟乙烯、六氟乙烯、偏氟乙烯的聚合物、四氟乙烯与六氟乙烯的共聚物中的一种或几种；优选为四氟乙烯；其中，含氟预聚体的聚合度小于等于50万，大于等于10万。
  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，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。
  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，所述三元共聚物选自本体聚合法、乳液聚合法、本体-悬浮聚合法制备的三元共聚物的一种或几种。
  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，所述三元共聚物，按重量份计，选自包含如下b.1在b.2上的接枝共聚物：
    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。
  9. 根据权利要求8所述的聚碳酸酯组合物，其特征在于，所述三元共聚物选自丙烯腈-苯乙烯共聚物AS、丙烯腈-丁二烯-苯乙烯三元共聚物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-苯乙烯三元共聚物MBS中的一种或几种；优选为丙烯腈-丁二烯-苯乙烯三元共聚物ABS和/或甲基丙烯酸甲酯-丁二烯-苯乙烯三元共聚物MBS；其中，MBS的粒径优选在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。
  10. 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，所述磷酸酯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1-3任一项所述的聚碳酸酯组合物，其特征在于，还包括其它助剂；所述其它助剂选自稳定剂、抗氧剂、阻燃增效剂、润滑剂、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：
    将聚碳酸酯、三元共聚物、磷酸酯阻燃剂、含磷预聚体、含氟预聚体、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。
PCT/CN2016/083635 2015-06-18 2016-05-27 一种聚碳酸酯组合物及其制备方法 WO2016202160A1 (zh)

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