WO2016202193A1 - 一种聚碳酸酯组合物及其制备方法与应用 - Google Patents

一种聚碳酸酯组合物及其制备方法与应用 Download PDF

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WO2016202193A1
WO2016202193A1 PCT/CN2016/085112 CN2016085112W WO2016202193A1 WO 2016202193 A1 WO2016202193 A1 WO 2016202193A1 CN 2016085112 W CN2016085112 W CN 2016085112W WO 2016202193 A1 WO2016202193 A1 WO 2016202193A1
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polycarbonate
perfluoro
parts
flame retardant
polycarbonate composition
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PCT/CN2016/085112
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English (en)
French (fr)
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杨燕
何继辉
佟伟
孙东海
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金发科技股份有限公司
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Publication of WO2016202193A1 publication Critical patent/WO2016202193A1/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
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a polycarbonate composition and a preparation method and application thereof.
  • polycarbonate As a kind of engineering plastic with excellent comprehensive performance, polycarbonate is widely used in mechanical and electronic lighting construction safety and medical equipment in various fields of national economy.
  • the use of flame-retardant fire-retardant polycarbonate materials can greatly increase the range of applications, and is widely used in office automation equipment, electrical machinery and electronic machinery, automobiles, and buildings. Polymers used in fields such as office automation equipment and electrical machinery and electromechanical machinery are required to have high flame retardancy.
  • a polycarbonate resin is made to have high flame retardancy by adding a flame retardant.
  • flame retardants include halogen flame retardants and halogen free flame retardants.
  • Halogen-based flame retardants include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy group Resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane or brominated aromatic crosslinked polymer, halogen-free flame retardant including nitrogen-containing flame retardant, Phosphorus-containing flame retardants, sulfonate flame retardants, etc.
  • JP-A 62199654 tetrabromobisphenol A oligomer is used to impart flame retardancy.
  • the compositions mentioned in US-A 2003/0069338 comprise in particular perfluorinated salts, silicones and certain UV absorbers. The same is true for WO 01/83606, in which a perfluorosulfonate is proposed.
  • U.S. Patent No. 3,775,367 discloses a flame retardant polycarbonate composition comprising an alkali metal or tetraalkylammonium salt of a perfluoroalkylsulfonic acid.
  • U.S. Patent No. 5,449,910 discloses flame retardant polycarbonate compositions comprising an alkali metal or alkaline earth metal salt of a perfluorocarbon sulfonic acid.
  • the inventors have surprisingly found through extensive experimentation that a specific content of a perfluoro-substituted polyolefin having a molecular weight of 400 ⁇ 10 4 to 500 ⁇ 10 4 and a total weight based on the polycarbonate composition are added to the polycarbonate composition formulation.
  • a specific content of a perfluoro-substituted polyolefin having a molecular weight of 400 ⁇ 10 4 to 500 ⁇ 10 4 and a total weight based on the polycarbonate composition are added to the polycarbonate composition formulation.
  • it is 5 ppm-100 ppm of perfluoro-substituted alkyl acid and its derivative
  • the stain resistance of the polycarbonate composition can be remarkably improved, and the fluidity retention rate and the flame retardancy retention rate are high, and it is particularly suitable for forming high-light light color. Electrical products.
  • Another object of the present invention is to provide a process for the preparation of the above polycarbonate composition.
  • a further object of the invention is to provide the use of the above polycarbonate compositions.
  • a polycarbonate composition comprising, by weight, the following composition:
  • the sum of the weight components of the three components a, b, and c is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight components of the three components a, b, and c is 100 parts;
  • the content of the perfluoro-substituted alkyl acid and its derivative in the total weight of the polycarbonate composition is from 5 ppm to 100 ppm.
  • the sample was cut into small pieces of about 1 cm 2 , and 20 g (accurate to 0.0001 g) sample was weighed, carbon tetrachloride/methanol was used as an extraction solvent, placed in a Soxhlet extraction cartridge, Soxhlet extraction for 16 hours, and the extract was filtered and purified. The mixture was dehydrated and concentrated over anhydrous sodium sulfate, and the volume was adjusted to 10 mL. The mobile phase was methanol and was subjected to liquid chromatography-mass spectrometry (LC-MS).
  • LC-MS liquid chromatography-mass spectrometry
  • Mass Spectrometry Condition Ion Source Negative Chemical Source (NCI). Ion source and quadrupole temperature: 150 °C. Determination method: Select ion scan (SIM), solvent delay: 315 min.
  • the perfluoro-substituted polyolefin having a molecular weight of from 400 ⁇ 10 4 to 500 ⁇ 10 4 has a melt index of from 1 g/10 min to 10 g/10 min measured at 372 ° C under a test condition of 5 kg according to the test method of ASTM D 1238.
  • the perfluoro-substituted polyolefin having a molecular weight of from 400 ⁇ 10 4 to 500 ⁇ 10 4 has a melting point of from 320 ° C to 330 ° C as measured according to ASTM D-4591.
  • the perfluoro-substituted polyolefin having a molecular weight of 400 ⁇ 10 4 to 500 ⁇ 10 4 is selected from the group consisting of polytetrafluoroethylene PTFE, a selected from the group consisting of polytetrafluoroethylene PTFE, perfluoro-substituted polyethylene propylene, and perfluoro-substituted polypropylene.
  • polytetrafluoroethylene PTFE a selected from the group consisting of polytetrafluoroethylene PTFE, perfluoro-substituted polyethylene propylene, and perfluoro-substituted polypropylene.
  • the perfluoro-substituted alkyl acid and its derivative have a water solubility of ⁇ 700 mg ⁇ L -1 as measured according to the OECD 105 method.
  • OECD 105 test method Weigh 2.5020g sample dissolved in 50mL pure water, shake at 30 °C for 24h, take it out and rest at 20 °C for 24h; filter, take 2mL of supernatant from each sample, measure it by UPLC-MS/MS concentration.
  • perfluoro-substituted alkyl acid and its derivative are selected from the group consisting of a perfluoro-substituted alkyl acid, a perfluoro-substituted alkyl acid halide, a perfluoro-substituted alkyl acid amino compound, and a perfluoro-substituted sulfonic acid.
  • the content of the perfluoro-substituted alkyl acid and its derivative in the total weight of the polycarbonate composition is from 10 ppm to 90 ppm, preferably from 15 ppm to 80 ppm; more preferably from 20 ppm to 50 ppm.
  • the polycarbonate is selected from the group consisting of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-fat One or more of a family polycarbonate, a branched polycarbonate, a siloxane copolycarbonate; 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 was calculated by using a solution of dichloromethane as a solvent at a test temperature of 25 ° C.
  • Bisphenol A and sodium hydroxide solution form bisphenol A sodium salt, which is sent to phosgenation reactor, and phosgene is introduced in the presence of dichloromethane solvent to react with bisphenol A sodium salt at the interface.
  • the low molecular weight polycarbonate was then polycondensed into a high molecular polycarbonate by adding triethylamine and caustic soda solution in a polycondensation kettle.
  • the polycarbonate resin may contain a resin prepared by transesterification of a phenol compound (for example, a dihydric phenol compound) and a carbonate precursor (for example, diphenyl carbonate).
  • 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 One or more of a perfluorotricyclopentadecane or a brominated aromatic crosslinked polymer;
  • the halogen-free flame retardant is selected from the group consisting of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant, and a nitrogen-containing and phosphorus-containing One or more of a flame retardant, a silicon-containing flame retardant
  • the polyester composition may further include 0-9.6 parts of rubber, and the rubber may be at least one selected from the group consisting of C 4 -C 6 diene rubber, (meth) acrylate rubber, and silicone rubber.
  • a rubber monomer; the rubber may also be a silicone rubber which comprises only a silicone rubber and/or a (meth) acrylate rubber, thereby improving the structural stability of the polycarbonate.
  • the polyester composition may further comprise 0-3 parts of other auxiliary agents; the other auxiliary agent is selected from one or more of an antioxidant, a light stabilizer, a lubricant, and a colorant.
  • the antioxidant is selected from one or more of a complex of phenols, phosphites, thioesters.
  • the light stabilizer can improve the photoaging resistance of the material during use, and can be selected from one or more compounds of hindered amines, benzotriazoles, and benzoxazinone complexes.
  • the lubricant is selected from one or more of a polyol ester, a metal soap, a stearic acid complex ester or an amide.
  • the coloring agent is selected from the group consisting of titanium dioxide, carbon black, phthalocyanine, ultramarine blue, azo, naphthalene ketone and the like. One or several of the toners.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • Polycarbonate, flame retardant, perfluoro-substituted polyolefin with a molecular weight of 400 ⁇ 10 4 -500 ⁇ 10 4 , perfluoro-substituted alkyl acid and its derivatives, and other additives are mixed in a high-mixing machine according to the ratio. Uniform, the speed of the mixer is from 450 rpm to 500 rpm, added to a twin-screw extruder, melt-mixed at a temperature of 240 ° C to 260 ° C, then granulated, cooled, and dried to obtain a polycarbonate. combination.
  • the polycarbonate compositions of the present invention are useful in the formation of high gloss, light colored electrical products.
  • the invention has the following beneficial effects:
  • the present invention employs the addition of a specific content of a perfluoro-substituted polyolefin having a molecular weight of from 400 ⁇ 10 4 to 500 ⁇ 10 4 in a polycarbonate composition formulation and a perfluoro substitution of from 5 ppm to 100 ppm based on the total weight of the polycarbonate composition.
  • a perfluoro-substituted polyolefin having a molecular weight of from 400 ⁇ 10 4 to 500 ⁇ 10 4 in a polycarbonate composition formulation and a perfluoro substitution of from 5 ppm to 100 ppm based on the total weight of the polycarbonate composition.
  • the end group in the polycarbonate resin is added to the polycarbonate resin to improve the stain resistance and hydrolytic stability, thereby significantly improving the stain resistance of the polycarbonate composition, and the fluidity retention ratio and High flame retardancy retention, especially suitable for forming high-light light-colored electrical products.
  • Test method for the content of perfluoro-substituted alkyl acid and its derivatives The sample is cut into small pieces of about 1 cm 2 , 20 g (accurate to 0.0001 g) sample is weighed, carbon tetrachloride/methanol is used as an extraction solvent, and placed in Soxhlet In the extraction filter cartridge, Soxhlet extraction for 16 hours, the extract was purified by filtration, dehydrated and concentrated through anhydrous sodium sulfate, and the volume was adjusted to 10 mL. The mobile phase was methanol, and liquid chromatography-mass spectrometry (LC-MS) was used. carry out testing.
  • LC-MS liquid chromatography-mass spectrometry
  • Mass Spectrometry Condition Ion Source Negative Chemical Source (NCI). Ion source and quadrupole temperature: 150 °C. Determination method: selective ion scanning (SIM), solvent delay: 315 min;
  • Test Method for Water Solubility was performed according to the OECD 105 method. Weigh 2.5020g The sample was dissolved in 50 mL of pure water, shaken at 30 ° C for 24 h, taken out and placed at 20 ° C for 24 h; filtered, each sample was taken 2 mL of the supernatant, and its concentration was determined by UPLC-MS/MS.
  • Test method for melt index ASTM D 1238, test condition is 372 ° C, 5 kg;
  • test strip thickness is 1.5mm
  • Fluidity test MFR according to the test ASTM D1238, the test conditions are 300 ° C, 1.2 kg;
  • the evaluation method of flame retardancy and fluidity is good or poor: when the flame retardant grade is constant, and the MFR change rate ⁇ 50% is judged to be good; if the flame retardant grade is changed or the MFR change rate is > 50%, it is judged to be poor.
  • Stain resistance test surface tension test: different dyne solution prepared with ethanol and water, coated with a cotton swab and a dyne solution on the surface of the flat plate (coating area > 3cm 2 ), such as If it does not shrink within 2 seconds, it can be reused with the higher value of the dyne solvent; if it shrinks within 2 seconds and breaks into many small droplets, it means that the number of the dyne solvent used last time is Plate surface tension. Evaluation method: When the surface tension ⁇ 44 dynes is judged to be good; when the surface tension > 44 dynes is judged to be poor.
  • the raw materials used in the examples and comparative examples are described below, but are not limited to these materials:
  • the polycarbonate used in the present invention is prepared as follows:
  • Bisphenol A and sodium hydroxide solution form bisphenol A sodium salt, which is sent to phosgenation reactor, and phosgene is introduced in the presence of dichloromethane solvent to react with bisphenol A sodium salt at the interface.
  • the low molecular weight polycarbonate was then polycondensed into a high molecular polycarbonate by adding triethylamine and caustic soda solution in a polycondensation kettle.
  • the polycarbonate resin may contain a resin prepared by transesterification of a phenol compound (for example, a dihydric phenol compound) and a carbonate precursor (for example, diphenyl carbonate).
  • KSS diphenyl sulfonate, METRO KSS, Metropolitan Eximchem Limited
  • PF1 is C 7 F 15 COOH (perfluorooctanoic acid, 3M);
  • the perfluoro-substituted polyolefin having a molecular weight of 400 ⁇ 10 4 to 500 ⁇ 10 4 used in the present invention :
  • PPF-1 is PTFE, molecular weight is 400 ⁇ 10 4 , melt index is 6g/10min, melting point is 325°C; (polytetrafluoroethylene, SOLVAY)
  • PPF-2 is PTFE, molecular weight is 500 ⁇ 10 4 , melt index is 6g/10min, melting point is 325°C;
  • PPF-3 is PTFE, molecular weight is 300 ⁇ 10 4 , melt index is 6g/10min, melting point is 325°C;
  • PPF-4 is PTFE, has a molecular weight of 600 ⁇ 10 4 , a melt index of 6 g/10 min, and a melting point of 325 ° C.
  • polycarbonate, flame retardant, perfluoro-substituted polyolefin with a molecular weight of 400 ⁇ 10 4 -500 ⁇ 10 4 , perfluoro-substituted alkyl acid and its derivatives are uniformly mixed in a high-mixer.
  • the speed of the mixer is from 450 rpm to 500 rpm, added to a twin-screw extruder, melt-mixed at a temperature of 240 ° C to 260 ° C, and then granulated, cooled, and dried to obtain a polycarbonate composition.
  • the flowability and retention of the polycarbonate composition, flame retardancy and retention, and stain resistance were tested.
  • the data is shown in Table 1.
  • the total weight of the carbonate composition is from 5 ppm to 100 ppm of the perfluoro-substituted alkyl acid and the derivative thereof, since the fluorine atom is large in volume and the negative charge of the fluorine atom of the adjacent macromolecule has a repulsive action, the fluoride cohesive force is low, It is not easily stained, and its negative charge of fluorine atoms enables it to stabilize the end groups in the polycarbonate resin, and is added to the polycarbonate resin to improve the stain resistance and hydrolytic stability, thereby significantly increasing the aggregation.
  • the carbonate composition has high stain resistance and high fluidity retention and flame retardancy retention, and is particularly suitable for molding high-light light-colored electrical products.

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Abstract

一种聚碳酸酯组合物，按重量份计，包括以下组成： a、86份-99.7份的聚碳酸酯； b、0.2份-1份的分子量为400×10 4-500×10 4的全氟取代聚烯烃； c、0.1份-13.8份的阻燃剂；其中，a、b、c三种组分的重量份之和为100份。通过选用在聚碳酸酯组合物配方中添加特定含量的分子量为400×10 4-500×10 4的全氟取代聚烯烃以及基于聚碳酸酯组合物的总重量为5ppm-100ppm的全氟取代烷基酸及其衍生物时，能够明显提高聚碳酸酯组合物的耐玷污性，且流动性保持率和阻燃性保持率高，特别适用于成型高光浅色电工产品。

Description

一种聚碳酸酯组合物及其制备方法与应用 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与应用。
背景技术
聚碳酸酯作为一种综合性能优异的工程塑料，在国民经济各领域中广泛的用于机械电子电器照明建筑安全以及医疗器械方面。采用阻燃防火级聚碳酸酯材料，可以大幅提高其应用范围，并且广泛用于办公自动化设备、电力机械和电子机械、机动车、以及建筑物等多种领域。在如办公自动化设备和电力机械及电子机械领域中使用的聚合物需要具有高阻燃性。
通常，通过加入阻燃剂来使聚碳酸酯树脂具有高阻燃性。这些阻燃剂包括卤系阻燃剂和无卤阻燃剂。卤系阻燃剂包括溴化聚苯乙烯、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等，无卤阻燃剂包括含氮阻燃剂、含磷阻燃剂、磺酸盐阻燃剂等。
表面能是影响抗沾污材料性能的重要因素之一，表面能越小，就越不容易被一些液体所浸润。因此，制备低表面能的材料是制备疏水抗沾污材料的前提条件。然而添加阻燃剂会不同程度地提高材料的表面能，在一些高光白色电工制品中无法满足不沾污的要求。因此，亟需找到一种既满足阻燃要求，又具有良好耐沾污性的材料。
JP-A62199654中，使用四溴双酚A低聚物赋予阻燃性。US-A2003/0069338中提到的组合物尤其包含全氟化盐、硅酮和某些紫外线吸收剂。WO01/83606同样如此，其中提出全氟磺酸盐。美国专利3775367公开了包含全氟烷基磺酸的碱金属盐或四烷基铵盐的阻燃聚碳酸酯组合物。美国专利5449710公开了包含全氟烃类磺酸的碱金属盐或碱土金属盐的阻燃聚碳酸酯组合物。
但是，在湿热条件下，即使含有这些优异阻燃剂的材料的阻燃性及机械性能也会损失严重。此外，未有文献及研究公开如何提高阻燃聚碳酸酯材料的耐沾污 性及耐水解性。
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分子量为400×104-500×104的全氟取代聚烯烃以及基于聚碳酸酯组合物的总重量为5ppm-100ppm的全氟取代烷基酸及其衍生物时，能够明显提高聚碳酸酯组合物的耐玷污性，且流动性保持率和阻燃性保持率高，特别适用于成型高光浅色电工产品。
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优异的耐玷污性，且流动性保持率和阻燃性保持率高的聚碳酸酯组合物。
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。
本发明的再一目的是提供上述聚碳酸酯组合物的用途。
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、86份-99.7份的聚碳酸酯；
b、0.2份-1份的分子量为400×104-500×104的全氟取代聚烯烃；
c、0.1份-13.8份的阻燃剂；
其中，a、b、c三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、90份-99.6份的聚碳酸酯；
b、0.3份-0.8份的分子量为400×104-500×104的全氟取代聚烯烃；
c、0.1份-9.7份的阻燃剂；
其中，a、b、c三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全氟取代烷基酸及其衍生物的含量为5ppm-100ppm。
全氟取代烷基酸及其衍生物的含量的测试方法：
样品剪成约1cm2的小片，称取20g(精确至0.0001g)样品，二氯化碳/甲醇作提取溶剂，置于索氏萃取滤筒中，索氏萃取16小时，萃取液经过滤净化后，并过无水硫酸钠脱水浓缩萃取、定容至10mL，流动相为甲醇，采用液相色谱- 质谱联用(LC-MS)进行测试。
色谱柱：HP-Innowax毛细管柱(30m×0.25mmi.d.,0.25μm)；柱温：50℃(5min)30℃Πmin 240℃(5min)；进样方式：不分流进样；接口温度：280℃；载气：高纯氦气(99.999％)；流速：0.8mLΠmin；进样量：1μL。
质谱条件离子源：负化学源(NCI)。离子源和四极杆温度：150℃。测定方式：选择离子扫描(SIM)，溶剂延迟：315min。
所述分子量为400×104-500×104的全氟取代聚烯烃根据ASTM D 1238的测试方法，在372℃，5kg的测试条件下测得的熔融指数为1g/10min-10g/10min。
所述分子量为400×104-500×104的全氟取代聚烯烃根据ASTM D-4591测得的熔点为320℃-330℃。
所述分子量为400×104-500×104的全氟取代聚烯烃选自聚四氟乙烯PTFE、选自聚四氟乙烯PTFE、全氟取代聚乙烯丙烯、全氟取代聚丙烯中的一种或几种，优选聚四氟乙PTFE。
其中，所述全氟取代烷基酸及其衍生物根据OECD 105方法测得的水溶解度≤700mg·L-1。
OECD 105测试方法：称取2.5020g样品溶于50mL纯水中，于30℃振荡24h后，取出置于20℃静止24h；过滤，各样品取上清液2mL，利用UPLC-MS/MS测定其浓度。
其中，所述全氟取代烷基酸及其衍生物选自全氟取代烷基酸、全氟取代烷基酸卤化物、全氟取代烷基酸氨基化合物、全氟取代磺酸中的一种或几种；优选为C8F17I、C8F17CH2CH2I、C8F17CH＝CH2、C4F9CH2CH2OH、C6F13CH2CH2OOCCH＝CH2、C8F17CH2CH2OOCC(CH3)＝CH2、C8F17CH2COOH、C7F15CF＝CHCOOH、C7F15COOH、C4F9SO2OH、C8H4F15NO2、C8F17SO2ONH3、C4F9I，C4F9CH2CH2OH、C7F15COOHNH3中的一种或几种；更优选为C4F9I，C4F9CH2CH2OH、C6F13CH2CH2OOCCH＝CH2、C7F15CF＝CHCOOH、C4F9SO2OH、C8F17I、C8F17SO2ONH3、C7F15COOH、C7F15COOHNH3中的一种或几种。
优选地，所述基于聚碳酸酯组合物的总重量中全氟取代烷基酸及其衍生物的含量为10ppm-90ppm，优选为15ppm-80ppm；更优选为20ppm-50ppm。
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：
双酚A与氢氧化钠溶液生成双酚A钠盐，送入光气化反应釜，在二氯甲烷溶剂存在的条件下通入光气，使其在界面上与双酚A钠盐反应生成低分子聚碳酸醋，然后在缩聚釜内加入三乙胺和烧碱溶液缩聚成高分子聚碳酸酯。此外，聚碳酸酯树脂可以包含通过酚化合物(例如，二元酚化合物)和碳酸酯前体(例如，碳酸二苯酯)的酯交换制备的树脂。
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；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、含硅阻燃剂、含硼阻燃剂、磺酸盐阻燃剂中的一种或几种。
该聚酯组合物中还可以包括0-9.6份的橡胶，橡胶可以为包含选自由C4-C6二烯橡胶、(甲基)丙烯酸酯橡胶、和硅橡胶所组成的组中的至少一种橡胶单体；橡胶也可以为通过仅包含硅橡胶和/或与(甲基)丙烯酸酯橡胶结合的硅橡胶，从而具有提高聚碳酸酯的结构稳定性。
该聚酯组合物中还可以进一步包括0-3份的其他助剂；所述其他助剂选自抗氧剂、光稳定剂、润滑剂、着色剂中的一种或几种。
所述抗氧剂选自酚类、亚磷酸酯类、硫代酯类的复合物中的一种或几种复配。
所述光稳定剂可以提高材料在使用过程中的耐光老化性能，可选自受阻胺类、苯并三唑类、苯并噁嗪酮类复合物中的一种或几种复配。
所述润滑剂选自多元醇酯类、金属皂、硬脂酸复合酯或酰胺类中的一种或几种。
所述着色剂选自钛白粉、炭黑、酞菁、群青、偶氮、萘环酮等无机及有机着 色剂中的一种或几种。
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、阻燃剂、分子量为400×104-500×104的全氟取代聚烯烃、全氟取代烷基酸及其衍生物、其它助剂按照配比在高混机中混合均匀，混合机的转速为450转/分钟-500转/分钟，加入到双螺杆挤出机中，在240℃-260℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物。
本发明的聚碳酸酯组合物可应用于成型高光浅色电工产品。
本发明与现有技术相比，具有如下有益效果：
本发明选用在聚碳酸酯组合物配方中添加特定含量的分子量为400×104-500×104的全氟取代聚烯烃以及基于聚碳酸酯组合物的总重量为5ppm-100ppm的全氟取代烷基酸及其衍生物时，由于氟原子体积大且相邻大分子的氟原子负电荷有相斥作用，使得氟化物内聚力低，不易沾污，且其氟原子负电荷作用使其能够稳定聚碳酸酯树脂中的端基，添加到聚碳酸酯树脂中，起到提高耐玷污性和水解稳定性的作用，从而能够明显提高聚碳酸酯组合物的耐玷污性，且流动性保持率和阻燃性保持率高，特别适用于成型高光浅色电工产品。
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：
全氟取代烷基酸及其衍生物的含量的测试方法：样品剪成约1cm2的小片，称取20g(精确至0.0001g)样品，二氯化碳/甲醇作提取溶剂，置于索氏萃取滤筒中，索氏萃取16小时，萃取液经过滤净化后，并过无水硫酸钠脱水浓缩萃取、定容至10mL，流动相为甲醇，采用液相色谱-质谱联用(LC-MS)进行测试。
色谱柱：HP-Innowax毛细管柱(30m×0.25mmi.d.,0.25μm)；柱温：50℃(5min)30℃Πmin 240℃(5min)；进样方式：不分流进样；接口温度：280℃；载气：高纯氦气(99.999％)；流速：0.8mLΠmin；进样量：1μL。
质谱条件离子源：负化学源(NCI)。离子源和四极杆温度：150℃。测定方式：选择离子扫描(SIM)，溶剂延迟：315min；
水溶解度的测试方法：根据OECD 105方法进行水溶解度测试。称取2.5020g 样品溶于50mL纯水中，于30℃振荡24h后，取出置于20℃静止24h；过滤，各样品取上清液2mL，利用UPLC-MS/MS测定其浓度。
熔点的测试方法：ASTM D-4591；
熔融指数的测试方法：ASTM D 1238，测试条件为372℃，5kg；
阻燃测试：按照UL94标准，测试样条厚度为1.5mm；
流动性测试MFR：根据测定ASTM D1238，测试条件为300℃，1.2kg；
阻燃性以及流动性好或差的评估方法：当阻燃等级不变，且MFR变化率≤50％判定为好；如果阻燃等级变化或者MFR变化率＞50％判定为差。
耐沾污性测试：采用表面张力测试：采用乙醇和水配制好的不同达因溶液，用棉签蘸某一达因溶液在平放的方板表面涂布(涂布面积＞3cm2)，如在2秒钟内不收缩，可再使用标值较高达因溶剂重试；若在2秒钟内发生收缩，破裂成许多小液滴，则表明上一次使用的达因溶剂所标的数字就是该板表面张力。评估方法：当表面张力≤44达因判定为好；当表面张力＞44达因判定为差。现对实施例及对比例所用的原材料做如下说明，但不限于这些材料：
本发明中使用的聚碳酸酯按照下述方法制备：
双酚A与氢氧化钠溶液生成双酚A钠盐，送入光气化反应釜，在二氯甲烷溶剂存在的条件下通入光气，使其在界面上与双酚A钠盐反应生成低分子聚碳酸醋，然后在缩聚釜内加入三乙胺和烧碱溶液缩聚成高分子聚碳酸酯。此外，聚碳酸酯树脂可以包含通过酚化合物(例如，二元酚化合物)和碳酸酯前体(例如，碳酸二苯酯)的酯交换制备的树脂。
本发明中使用的阻燃剂：
KSS(二苯砜磺酸盐，METRO KSS，Metropolitan Eximchem Limited)；
本发明中使用的全氟取代烷基酸及其衍生物：
PF1为C7F15COOH(全氟辛酸，3M)；
PF2为C4F9I/C4F9CH2CH2OH＝1：1，(碘代氟丁烷，自制)；
本发明中使用的分子量为400×104-500×104的全氟取代聚烯烃：
PPF-1为PTFE，分子量为400×104，熔融指数为6g/10min，熔点为325℃；(聚四氟乙烯，SOLVAY)
PPF-2为PTFE，分子量为500×104，熔融指数为6g/10min，熔点为325℃；
PPF-3为PTFE，分子量为300×104，熔融指数为6g/10min，熔点为325℃；
PPF-4为PTFE，分子量为600×104，熔融指数为6g/10min，熔点为325℃。
实施例1-8及对比例1-8：聚碳酸酯组合物的制备
按表1的配方将聚碳酸酯、阻燃剂、分子量为400×104-500×104的全氟取代聚烯烃、全氟取代烷基酸及其衍生物在高混机中混合均匀，混合机的转速为450转/分钟-500转/分钟，加入到双螺杆挤出机中，在240℃-260℃的温度下进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物；对聚碳酸酯组合物的流动性及保持率、阻燃性及保持率和耐玷污性进行测试，数据见表1。
表1 实施例1-8及对比例1-8的具体配比(重量份)及其测试性能结果
Figure PCTCN2016085112-appb-000001
续表1
Figure PCTCN2016085112-appb-000002
Figure PCTCN2016085112-appb-000003
从表1的实施例和对比例的比较可以看出，本发明选用在聚碳酸酯组合物配方中添加特定含量的分子量为400×104-500×104的全氟取代聚烯烃以及基于聚碳酸酯组合物的总重量为5ppm-100ppm的全氟取代烷基酸及其衍生物时，由于氟原子体积大且相邻大分子的氟原子负电荷有相斥作用，使得氟化物内聚力低，不易沾污，且其氟原子负电荷作用使其能够稳定聚碳酸酯树脂中的端基，添加到聚碳酸酯树脂中，起到提高耐玷污性和水解稳定性的作用，从而能够明显提高聚碳酸酯组合物的耐玷污性，且流动性保持率和阻燃性保持率高，特别适用于成型高光浅色电工产品。

Claims (14)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、86份-99.7份的聚碳酸酯；
    b、0.2份-1份的分子量为400×104-500×104的全氟取代聚烯烃；
    c、0.1份-13.8份的阻燃剂；
    其中，a、b、c三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、90份-99.6份的聚碳酸酯；
    b、0.3份-0.8份的分子量为400×104-500×104的全氟取代聚烯烃；
    c、0.1份-9.7份的阻燃剂；
    其中，a、b、c三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全氟取代烷基酸及其衍生物的含量为5ppm-100ppm。
  3. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述分子量为400×104-500×104的全氟取代聚烯烃根据ASTM D 1238的测试方法，在372℃，5kg的测试条件下测得的熔融指数为1g/10min-10g/10min。
  4. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述分子量为400×104-500×104的全氟取代聚烯烃根据ASTM D-4591测得的熔点为320℃-330℃。
  5. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，所述分子量为400×104-500×104的全氟取代聚烯烃选自聚四氟乙烯PTFE、全氟取代聚乙烯丙烯、全氟取代聚丙烯中的一种或几种，优选为聚四氟乙烯PTFE。
  6. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述全氟取代烷基酸及其衍生物根据OECD 105方法测得的水溶解度≤700mg·L-1。
  7. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述全氟取代烷基酸及其衍生物选自全氟取代烷基酸、全氟取代烷基酸卤化物、全氟取代烷基酸氨基化合物、全氟取代磺酸中的一种或几种；优选为C8F17I、C8F17CH2CH2I、C8F17CH＝CH2、C4F9CH2CH2OH、C6F13CH2CH2OOCCH＝CH2、 C8F17CH2CH2OOCC(CH3)＝CH2、C8F17CH2COOH、C7F15CF＝CHCOOH、C7F15COOH、C4F9SO2OH、C8H4F15NO2、C8F17SO2ONH3、C4F9I，C4F9CH2CH2OH、C7F15COOHNH3中的一种或几种；更优选为C4F9I，C4F9CH2CH2OH、C6F13CH2CH2OOCCH＝CH2、C7F15CF＝CHCOOH、C4F9SO2OH、C8F17I、C8F17SO2ONH3、C7F15COOH、C7F15COOHNH3中的一种或几种。
  8. 根据权利要求2所述的聚碳酸酯组合物，其特征在于，所述基于聚碳酸酯组合物的总重量中全氟取代烷基酸及其衍生物的含量为10ppm-90ppm，优选为15ppm-80ppm；更优选为20ppm-50ppm。
  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。
  10. 根据权利要求9所述的聚碳酸酯组合物，其特征在于，所述芳香族聚碳酸酯选自粘均分子量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。
  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；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、含硅阻燃剂、含硼阻燃剂、磺酸盐阻燃剂中的一种或几种。
  12. 根据权利要求1或2所述的聚碳酸酯组合物，其特征在于，还包括0-9.6份的橡胶和0-3份的其他助剂，所述其他助剂选自抗氧剂、光稳定剂、润滑剂、着色剂中的一种或几种。
  13. 如权利要求1-12一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、阻燃剂、分子量为400×104-500×104的全氟取代聚烯烃、全氟取代烷基酸及其衍生物、其它助剂按照配比在高混机中混合均匀，混合机的转速为450转/分钟-500转/分钟，加入到双螺杆挤出机中，在240℃-260℃的温度下 进行熔融混合，然后造粒、冷却、干燥得到聚碳酸酯组合物。
  14. 如根据权利要求1-12任一项所述的聚碳酸酯组合物在成型高光浅色电工产品的应用。
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