WO2016202192A1 - 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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WO2016202192A1
WO2016202192A1 PCT/CN2016/085109 CN2016085109W WO2016202192A1 WO 2016202192 A1 WO2016202192 A1 WO 2016202192A1 CN 2016085109 W CN2016085109 W CN 2016085109W WO 2016202192 A1 WO2016202192 A1 WO 2016202192A1
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polycarbonate
flame retardant
parts
polycarbonate composition
perfluoro
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French (fr)
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杨燕
何继辉
佟伟
孙东海
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Kingfa Science and Technology Co Ltd
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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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

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 flame retardant materials are widely used in the charger and battery industry due to their excellent performance, but the flame retardant properties and mechanical properties of polycarbonate flame retardant materials in wet environments will be greatly reduced, which cannot meet the high temperature requirements of these industries. Industry requirements for wet conditions.
  • 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 perfluorosulfonate is disclosed.
  • the inventors have surprisingly found through extensive experimentation that the content of the perfluoro-substituted alkyl acid and its derivative added in the polycarbonate composition formulation is ⁇ 100 ppm based on the total weight of the polycarbonate composition, due to the perfluoro-substituted alkane.
  • the base acid and its derivatives have low water solubility and are not easily ineffective in the presence of water, and can significantly improve the mechanical properties and flame retardancy of the polycarbonate composition under high temperature and high humidity conditions, and the flame retardancy reaches 1.5 mm/ V-0, high mechanical and flame retardant retention at 85% humidity and 85°C, and is especially suitable for molding chargers and battery industries.
  • 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 fractions of the two components a and b is 100 parts.
  • a polycarbonate composition by weight, comprises the following composition:
  • the sum of the weight fractions of the two components a and b 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.
  • 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, and then dehydrated and concentrated by sodium sulfate, and the volume was adjusted to 10 mL. The mobile phase was methanol and tested by 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 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.
  • the perfluoro-substituted alkyl acid and its derivative are based on the total weight of the polycarbonate composition
  • the content is from 10 ppm to 90 ppm, preferably from 15 ppm to 80 ppm; more preferably from 20 ppm to 50 ppm.
  • the perfluoro-substituted alkyl acid and its derivative are selected from one or more 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 polycarbonate is selected from one or the group consisting 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 aromatic polycarbonate has 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 comprise 0 to 4.9 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.
  • 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 agents are selected from one or more of an antioxidant, a light stabilizer, an anti-drip agent, a lubricant, and a colorant.
  • the other auxiliary agents are selected from one or more of an antioxidant, a light stabilizer, an anti-drip agent, a lubricant, and a colorant.
  • the anti-drip agent is selected from the group consisting of polytetrafluoroethylene, pure polytetrafluoroethylene powder, AS coated modified polytetrafluoroethylene powder, and PMMA coated modified polytetrafluoroethylene powder. .
  • 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 colorant is selected from one or more of inorganic and organic colorants such as titanium dioxide, carbon black, phthalocyanine, ultramarine blue, azo, naphthalenone, and the like.
  • the preparation method of the above polycarbonate composition comprises the following steps:
  • the polycarbonate resin, the flame retardant, the perfluoro-substituted alkyl acid and the derivative thereof are uniformly mixed in a high-mixer, and the speed of the mixer is 450 rpm to 500 rpm, and the mixture is added to the twin-screw extruder.
  • melt-mixing is carried out at a temperature of from 240 ° C to 260 ° C, followed by granulation, cooling, and drying to obtain a polycarbonate composition.
  • the polycarbonate compositions of the present invention are useful in the molding charger and battery industries.
  • the invention has the following beneficial effects:
  • the present invention is characterized in that the content of the perfluoro-substituted alkyl acid and its derivative added in the polycarbonate composition formulation is ⁇ 100 ppm based on the total weight of the polycarbonate composition, and the water is replaced by the perfluoro-substituted alkyl acid and its derivative.
  • Low solubility not easy to fail in the presence of water, can significantly improve the mechanical properties and flame retardant properties of polycarbonate compositions under high temperature and high humidity conditions, and its flame retardant performance reaches 1.5mm/v-0, at 85% humidity And 85 ° C, mechanical properties and flame retardant retention rate, and is particularly suitable for molding chargers and battery industry.
  • 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. , dehydrated and concentrated with sodium sulfate, and concentrated to 10 mL.
  • the mobile phase was methanol and tested by liquid chromatography-mass spectrometry (LC-MS).
  • 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.
  • Test Method for Water Solubility was performed according to the OECD 105 method. 2.5020 g of 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.
  • Tensile strength determined according to ISO 527-2, the test conditions are 23 ° C, 50 mm / min;
  • Tensile strength retention rate tensile strength (after boiled or damp heat aging) / tensile strength ⁇ 100%;
  • Cantilever notched impact strength measured according to ISO 180;
  • Impact strength retention rate tensile strength (after boiled or damp heat aging) / impact strength ⁇ 100%;
  • test strip thickness is 1.5mm
  • Flame-retardant boiling test according to UL746C, the test condition is 70 ° C, 7 days, the medium is deionized water;
  • the polycarbonate used in the present invention is prepared as follows:
  • the carbonate 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 of Example 1 is KSS (diphenyl sulfone sulfonate, METRO KSS, Metropolitan Eximchem Limited);
  • the flame retardant of Example 2 and Example 7 to Example 10 is BDP (bisphenol A bis(diphenyl phosphate); FP-600, Edike);
  • the flame retardant of Example 3 - Example 6 is FG-8500 (tetrabromobisphenol A-polycarbonate oligomer, Teijin);
  • the flame retardant of Comparative Example 1 is KSS;
  • the flame retardant of Comparative Example 2 is BDP;
  • the flame retardant of Comparative Example 3 is BDP;
  • the flame retardant of Comparative Example 4 to Comparative Example 7 was BDP.
  • PF1 is C 7 F 15 COOH, water solubility is 600 mg ⁇ L -1 (perfluorooctanoic acid, 3 M);
  • PF3 is C 4 F 9 SO 2 OH, water solubility is 350 mg ⁇ L -1 (perfluorobutyl sulfonic acid, homemade);
  • PF4 is C 4 F 9 CH 2 CH 2 SO 3 K, water solubility is 350 mg ⁇ L -1 (potassium perfluoropentyl sulfonate, homemade);
  • PF5 is C 7 F 15 COOH, water solubility is 750 mg ⁇ L -1 (perfluorooctanoic acid, 3 M);
  • the polycarbonate, flame retardant, perfluoro-substituted alkyl acid and its derivatives are uniformly mixed in a high-mixer, and the speed of the mixer is from 450 rpm to 500 rpm, and is added to the double.
  • melt-mixing is carried out at a temperature of 240 ° C to 260 ° C, followed by granulation, cooling, and drying to obtain a polycarbonate composition; tensile strength and retention of the polycarbonate composition, and cantilever gap The impact strength and retention, flame retardancy and retention were tested.
  • Table 1 The data is shown in Table 1.
  • the present invention selects the addition of perfluoro-substituted alkyl acid and its derivative content in the polycarbonate composition formulation to ⁇ 100 ppm based on the total weight of the polycarbonate composition.
  • the perfluoro-substituted alkyl acid and its derivatives have low water solubility, they are not easily ineffective in the presence of water, and the mechanical properties and flame retardancy of the polycarbonate composition under high temperature and high humidity conditions can be remarkably improved.
  • the flame retardant performance reaches 1.5mm/v-0. Under the conditions of 85% humidity and 85°C, the mechanical properties and flame retardant performance are high, and it is especially suitable for the molding charger and battery industry.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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、86份-99.9份的聚碳酸酯； b、0.1份-14份的阻燃剂；其中，a、b两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全氟取代烷基酸及其衍生物含量基于聚碳酸酯组合物的总重量中≤100ppm时，由于全氟取代烷基酸及其衍生物的水溶解度低，在水存在条件下不易失效，能够明显提高聚碳酸酯组合物在高温高湿条件下的机械性能和阻燃性能，其阻燃性能达到1.5mm/v-0，在85％湿度和85℃条件下，机械性能及阻燃性能保持率高，且特别适用于成型充电器及电池行业。

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
聚碳酸酯阻燃材料由于其优异的性能，广泛应用于充电器及电池行业，但是在潮湿环境下聚碳酸酯阻燃材料的阻燃性能及机械性能会大大降低，不能满足这些行业需要高温高湿条件的行业要求。
大量文献描述了如何改进芳族聚碳酸酯树脂的阻燃性的方法，这些方法包括添加卤系阻燃剂或无卤阻燃剂。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。
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，其中公开了全氟磺酸盐。
但是，到目前为止，关于在聚碳酸酯树脂配方中添加哪种添加剂或添加剂混合物对所述聚碳酸酯树脂能够在长期湿热后也能保持良好的机械性能及阻燃性还未见报道；此外，也没有文献提到如何提高阻燃聚碳酸酯树脂的耐水解性。
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全氟取代烷基酸及其衍生物含量基于聚碳酸酯组合物的总重量中≤100ppm时，由于全氟取代烷基酸及其衍生物的水溶解度低，在水存在条件下不易失效，能够明显提高聚碳酸酯组合物的在高温高湿条件下的机械性能和阻燃性能，其阻燃性能达到1.5mm/v-0，在85％湿度和85℃条件下，机械性能及阻燃性能保持率高，且特别适用于成型充电器及电池行业。
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在高温高湿条件下机械性能和阻燃性能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-99.9份的聚碳酸酯；
b、0.1份-14份的阻燃剂；
其中，a、b两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、95份-99.9份的聚碳酸酯；
b、0.1份-5份的阻燃剂；
其中，a、b两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，再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。
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。
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。
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。
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一种；优选为芳香族聚碳酸酯。
优选地，所述芳香族聚碳酸酯的粘均分子量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0-4.9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、抗滴落剂、润滑剂、着色剂中的一种或几种。
所述抗滴落剂选自聚四氟乙烯、纯聚四氟乙烯粉、AS包覆改性的聚四氟乙烯粉、PMMA包覆改性的聚四氟乙烯粉中的一种或几种。
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：
将聚碳酸酯树脂、阻燃剂、全氟取代烷基酸及其衍生物按比例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充电器及电池行业。
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全氟取代烷基酸及其衍生物含量基于聚碳酸酯组合物的总重量中≤100ppm时，由于全氟取代烷基酸及其衍生物的水溶解度低，在水存在条件下不易失效，能够明显提高聚碳酸酯组合物的在高温高湿条件下的机械性能和阻燃性能，其阻燃性能达到1.5mm/v-0，在85％湿度和85℃条件下，机械性能及阻燃性能保持率高，且特别适用于成型充电器及电池行业。
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，再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。
拉伸强度：根据ISO 527-2测定，测试条件为23℃，50mm/min；
拉伸强度保持率：拉伸强度保持率＝拉伸强度(水煮或湿热老化后)/拉伸强度×100％；
悬臂梁缺口冲击强度：根据ISO 180测定；
悬臂梁缺口冲击强度保持率：冲击强度保持率＝拉伸强度(水煮或湿热老化后)/冲击强度×100％；
阻燃测试：按照UL94标准，测试样条厚度为1.5mm；
阻燃性水煮测试：按照UL746C，测试条件为70℃，7天，介质为去离子水；
阻燃性湿热老化测试：按照ASTM D2126-04，测试条件为85℃，85％的湿度，1000小时。
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，然后在缩聚釜内加人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：
实施例1的阻燃剂为KSS(二苯砜磺酸盐，METRO KSS，Metropolitan Eximchem Limited)；
实施例2、实施例7-实施例10的阻燃剂为BDP(双酚A双(二苯基磷酸酯)；FP-600，艾迪科)；
实施例3-实施例6的阻燃剂为FG-8500(四溴双酚A-聚碳酸酯低聚物，帝人)；
对比例1的阻燃剂为KSS；
对比例2的阻燃剂为BDP；
对比例3的阻燃剂为BDP；
对比例4-对比例7的阻燃剂为BDP。
本发明中使用的全氟取代烷基酸及其衍生物：
PF1为C7F15COOH，水溶解度为600mg·L-1(全氟辛酸，3M)；
PF2为C4F9I/C4F9CH2CH2OH＝1：1，水溶解度为650mg·L-1(碘代氟丁烷，自制)；
PF3为C4F9SO2OH，水溶解度为350mg·L-1(全氟丁基磺酸，自制)；
PF4为C4F9CH2CH2SO3K，水溶解度为350mg·L-1(全氟戊基磺酸钾，自制)；
PF5为C7F15COOH，水溶解度为750mg·L-1(全氟辛酸，3M)；
实施例1-10及对比例1-7：聚碳酸酯组合物的制备
按表1的配方将聚碳酸酯、阻燃剂、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拉伸强度及保持率、悬臂梁缺口冲击强度及保持率、阻燃性能及保持率进行测试，数据见表1。
表1 实施例1-10及对比例1-7的具体配比(重量份)及其测试性能结果
[根据细则26改正07.07.2016]　
Figure WO-DOC-TABLE-1
[根据细则26改正07.07.2016]　
续表1
[根据细则26改正07.07.2016]　
Figure WO-DOC-TABLE-2
[根据细则26改正07.07.2016]　
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全氟取代烷基酸及其衍生物含量基于聚碳酸酯组合物的总重量中≤100ppm时，由于全氟取代烷基酸及其衍生物的水溶解度低，在水存在条件下不易失效，能够明显提高聚碳酸酯组合物的在高温高湿条件下的机械性能和阻燃性能，其阻燃性能达到1.5mm/v-0，在85％湿度和85℃条件下，机械性能及阻燃性能保持率高，且特别适用于成型充电器及电池行业。

Claims (11)

  1. 一种聚碳酸酯组合物，按重量份计，包括以下组成：
    a、86份-99.9份的聚碳酸酯；
    b、0.1份-14份的阻燃剂；
    其中，a、b两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、95份-99.9份的聚碳酸酯；
    b、0.1份-5份的阻燃剂；
    其中，a、b两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。
  4. 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。
  5. 根据权利要求2-4任一项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。
  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一种；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选自粘均分子量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。
  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。
  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，还包括0-4.9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、抗滴落剂、润滑剂、着色剂中的一种或几种。
  10. 如权利要求1-9任一项所述的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、全氟取代烷基酸及其衍生物按比例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。
  11. 如根据权利要求1-9任一项所述的聚碳酸酯组合物在成型充电器及电池的应用。
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CN104962058A (zh) * 2015-06-18 2015-10-07 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法与应用
CN104962057A (zh) * 2015-06-18 2015-10-07 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法与应用
CN104962060A (zh) * 2015-06-18 2015-10-07 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法与应用

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CN116041933A (zh) * 2023-01-17 2023-05-02 中山诗兰姆汽车零部件有限公司 一种无卤耐高温阻燃abs复合pc合金材料及其制备方法与应用
CN116041933B (zh) * 2023-01-17 2024-05-17 中山诗兰姆汽车零部件有限公司 一种无卤耐高温阻燃abs复合pc合金材料及其制备方法与应用

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