WO2020151552A1 - 聚碳酸酯组合物和磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用 - Google Patents

聚碳酸酯组合物和磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用 Download PDF

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WO2020151552A1
WO2020151552A1 PCT/CN2020/072285 CN2020072285W WO2020151552A1 WO 2020151552 A1 WO2020151552 A1 WO 2020151552A1 CN 2020072285 W CN2020072285 W CN 2020072285W WO 2020151552 A1 WO2020151552 A1 WO 2020151552A1
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sulfonate
bis
parts
phosphorus
polycarbonate
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French (fr)
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吴俊�
佟伟
黄险波
叶南飚
李明昆
彭民乐
杨燕
丁超
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • 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
    • C08K5/49—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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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

Definitions

  • the present invention relates to the technical field of polymer materials, in particular to the application of polycarbonate compositions and sulfonates and phosphorus-containing compounds to reduce fuming and heat release of polycarbonates.
  • PC Polycarbonate
  • Cide patent CN104830041A discloses a low heat release polycarbonate material, the main components of which are brominated flame retardant, semi-aromatic polyester, and silicone polycarbonate.
  • brominated flame retardant is not advocated under the current trend of pursuing environmental protection, and the smoke produced by brominated flame retardants is usually very toxic, which is not good for people to escape in confined spaces. And the patent does not discuss the effect of reducing smoke.
  • the halogen-free polymer system in the prior art focuses on optimizing the formulation by evaluating the flame retardant rating, but less attention is paid to the amount of smoke emitted. 85% of the casualties in the fire are caused by smoke, so it is necessary to study the polymerization Smoke generation of the material system. Because the combustion mechanism and smoke generation mechanism of polymers are completely different, and when flame retardants are added to the polymer, the combustion is more incomplete and usually aggravates the amount of smoke generation. Therefore, it is difficult for the polymer to have both good smoke suppression and smoke suppression effects. Flame retardant effect. In order to solve these two technical problems at the same time, the existing polymer molding materials need to add one or more synergists in the preparation process to achieve flame retardant and smoke suppression effects.
  • the object of the present invention is to provide a polycarbonate composition, which has the advantages of low smoke, low heat release and good toughness during high temperature or combustion.
  • Another object of the present invention is to provide applications of sulfonates and phosphorus-containing compounds in reducing the density and heat release rate of polycarbonate smoke.
  • a polycarbonate composition in parts by weight, comprising the following components:
  • the phosphorus-containing compound is selected from hexaphenoxy ring triphosphazene, bisphenol A-bis(diphenyl phosphate), resorcinol bis[bis(2,6-dimethylphenyl phosphate)], At least one of triphenylphosphine oxide.
  • phosphorus-containing compounds and sulfonate compounds can also reduce smoke density and heat release rate, but hexaphenoxy ring triphosphazene, bisphenol A-bis (diphenyl phosphate), resorcinol bis [ Di(2,6-Dimethylphenyl phosphate)] and triphenylphosphine oxide have the best effect, and can prepare polycarbonate compositions with excellent low smoke density and heat release rate at a small addition amount.
  • Hexaaminocyclotriphosphazene and hexaphenylaminocyclotriphosphazene have a greater impact on the mechanical properties of polycarbonate, and because they contain more nitrogen-containing groups, more toxic and harmful nitrogen oxides will be produced during the combustion process;
  • Linear polyphosphazenes such as (4-carboxyphenoxy) phosphazene have poor compatibility with polycarbonate, and the effect of actually reducing smoke density and heat release rate is not as good as hexaphenoxy ring triphosphazene and bisphenol A-Bis(diphenyl phosphate), resorcinol bis[bis(2,6-dimethylphenyl phosphate)] or triphenylphosphine oxide is good.
  • the most commonly used mineral filler in polycarbonate is talc, which also has certain flame retardant properties.
  • talc which also has certain flame retardant properties.
  • the choice of mineral fillers should not only consider low smoke density and low heat release rate, but also Good toughness is maintained.
  • the present invention finds that the addition of boehmite has a good balance between toughness, smoke density and heat release rate, which is beneficial to the preparation of polycarbonate compositions with good comprehensive properties.
  • the polycarbonate resin of the present invention may be a branched thermoplastic polymer or copolymer obtained by the reaction of a dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester.
  • the production method of the polycarbonate resin is not particularly limited, and the polycarbonate resin produced by the hitherto known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used.
  • bisphenol A 2,2-bis(4-hydroxyphenyl)propane
  • tetramethylbisphenol A bis(4-hydroxyphenyl) )-P-diisopropylbenzene
  • hydroquinone resorcinol
  • 4,4-dihydroxydiphenyl etc.
  • a compound in which at least one tetraalkylphosphonium sulfonate is bonded to the aforementioned aromatic dihydroxy compound can also be used.
  • the polycarbonate resin is preferably an aromatic polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane, or from 2,2-bis(4-hydroxyphenyl)propane and other aromatics.
  • the polycarbonate resin may also be a copolymer in which the main composition is an aromatic polycarbonate resin, for example, a copolymer with a siloxane structure-containing polymer or oligomer.
  • a mixture of two or more of the aforementioned polycarbonate resins may be used.
  • Monovalent aromatic hydroxy compounds can be used to adjust the molecular weight of polycarbonate resins, for example, m-cresol, p-cresol, m-propyl phenol, p-propyl phenol, p-tert-butyl phenol and p-(long chain alkyl )-Substituted phenol.
  • the present invention has no particular limitation on the production method of the polycarbonate resin, and the polycarbonate resin produced by the phosgene method (interfacial polymerization method) or the melting method (transesterification method) can be used.
  • the polycarbonate resin is also provided by subjecting a polycarbonate resin produced by a melt method to a post-treatment for adjusting the amount of terminal hydroxyl groups.
  • the sulfonate is selected from at least one of tetraethylammonium perfluoroethanesulfonate, potassium diphenylsulfone sulfonate, potassium perfluoroalkylsulfonate, potassium benzenesulfonylbenzenesulfonate, and sodium p-toluenesulfonate
  • tetraethylammonium perfluoroethanesulfonate potassium diphenylsulfone sulfonate, potassium perfluoroalkylsulfonate, potassium benzenesulfonylbenzenesulfonate, and sodium p-toluenesulfonate
  • the sulfonate is selected from potassium perfluorobutanesulfonate.
  • the phosphorus-containing compound is selected from at least one of hexaphenoxy ring triphosphazene and resorcinol bis[bis(2,6-dimethylphenyl phosphate)]; the boehmite
  • the particle size ranges from 0.1 microns to 13 microns. Further, the particle size of the mineral filler is 0.1 to 13 microns.
  • the particle size of the mineral filler is less than 0.1 microns, the surface area is too large, and the degradation effect of the polycarbonate is greatly improved under the same amount of addition, and because the particle size is too small, it is easy to agglomerate and bring difficulties to processing; When the filler particle size is greater than 13 microns, the mechanical properties are insufficient.
  • the particle size of the filler used in the production and testing process is generally distributed in a certain range, such as 4-6 microns, or a wider range of 3-7 microns.
  • the composition In order to increase the anti-dripping performance of the composition when it is burned or subjected to high temperatures, it also includes 0-5 parts by weight of an anti-dripping agent in parts by weight; the anti-dripping agent is selected from polytetrafluoroethylene and silicone At least one of coated polytetrafluoroethylene, methacrylate polymer coated polytetrafluoroethylene, and styrene-acrylonitrile copolymer coated polytetrafluoroethylene.
  • the polycarbonate composition can also include 0-10 parts by weight of auxiliary agents; the auxiliary agents are heat stabilizers, antioxidants, light stabilizers, plasticizers, fillers and colorants. At least one.
  • the lubricant is metal stearate lubricant, alkyl stearate lubricant, pentaerythritol stearate lubricant, paraffin wax or montan wax.
  • the heat stabilizer is an organic phosphite, preferably triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylbenzene Phosphonate or trimethyl phosphate.
  • the antioxidant is an organic phosphite, an alkylated monohydric phenol or polyhydric phenol, an alkylation reaction product of a polyhydric phenol and a diene, a butylation reaction product of p-cresol or dicyclopentadiene, alkane Alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds or polyol ester antioxidants.
  • the light stabilizer is at least one of a benzotriazole light stabilizer or a benzophenone light stabilizer.
  • the plasticizer is phthalate.
  • the colorant is a pigment or dye.
  • the preparation method of the above polycarbonate composition includes the following steps: weigh the polycarbonate, sulfonate, phosphorus-containing compound, boehmite, and auxiliaries according to the proportions, then mix them in a high-speed mixer, and then put them in Extrusion and granulation in a twin-screw extruder to obtain a polycarbonate composition.
  • the application of sulfonates and phosphorus-containing compounds in reducing the fuming and heat release of polycarbonate, by weight, includes the following components:
  • Phosphorus-containing compounds 2-10 copies Phosphorus-containing compounds 2-10 copies.
  • the amount of the phosphorus-containing compound can be any number of parts from 2, 3, 4, to 12 parts.
  • the change of smoke release and heat release rate first decreases and then rises.
  • the smoke release density and heat release rate are comprehensively controlled, and the toughness is less attenuated.
  • excessive addition of the sulfonate will also cause the toughness of the composition to decrease.
  • the sulfonate is selected from at least one of tetraethylammonium perfluoroethanesulfonate, potassium diphenylsulfone sulfonate, potassium perfluoroalkylsulfonate, potassium benzenesulfonylbenzenesulfonate, and sodium p-toluenesulfonate
  • tetraethylammonium perfluoroethanesulfonate potassium diphenylsulfone sulfonate, potassium perfluoroalkylsulfonate, potassium benzenesulfonylbenzenesulfonate, and sodium p-toluenesulfonate
  • the sulfonate is selected from potassium perfluorobutanesulfonate.
  • the phosphorus-containing compound may be hexaphenoxy ring triphosphazene, triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), resorcinol bis [Di(2,6-dimethylphenyl phosphate)], at least one of triphenylphosphine oxide.
  • the phosphorus-containing compound is selected from the group consisting of hexaphenoxy ring triphosphazene, bisphenol A-bis(diphenyl phosphate), resorcinol bis[bis(2,6-dimethylphenyl phosphate) )], at least one of triphenylphosphine oxide.
  • the mineral filler is selected from talc, titanium dioxide, mica, zinc sulfide, calcium carbonate, barium sulfate, magnesium sulfate, magnesium hydroxide, boron nitride, and Mongolia At least one of clay, kaolin, boehmite, and zinc borate;
  • the mineral filler is selected from at least one of mica and zinc borate; mica and zinc borate have the best effects in reducing smoke density and heat release rate.
  • the particle size of the mineral filler is 0.1 to 13 microns.
  • the present invention finds that the combination of sulfonate and phosphorus-containing compound can also effectively reduce the smoke release density and heat release rate of the polycarbonate composition.
  • it can Effectively reduce the amount of mineral fillers, so the toughness of the material is also well maintained.
  • the raw materials used in the present invention are all derived from commercially available products.
  • Sulfonate A potassium perfluorobutane sulfonate
  • Sulfonate B potassium benzenesulfonylbenzenesulfonyl
  • Phosphorus-containing compound A resorcinol bis[bis(2,6-dimethylphenyl phosphate)];
  • Phosphorus-containing compound B Bisphenol A-bis(diphenyl phosphate);
  • Boehmite particle size of 4-6 microns
  • Mica particle size of 4-6 microns
  • Zinc borate particle size 4-6 microns
  • Anti-dripping agent styrene-acrylonitrile copolymer coated with polytetrafluoroethylene
  • Lubricant LOXIOL P 861/3.5;
  • Antioxidant CHINOX 10766;
  • the preparation method of the polycarbonate composition of the embodiment and the comparative example weigh the polycarbonate, sulfonate, phosphorus-containing compound, mineral filler, and anti-dripping agent according to the proportion, mix them evenly in a high-speed mixer, and then put in the double
  • the polycarbonate composition was obtained by extruding and granulating in a screw extruder.
  • Table 1 The proportions (parts by weight) of the polycarbonate compositions of Examples 1-6 and Comparative Examples 1-3 and various performance test results
  • Example 3/5 It can be seen from Example 3/5 that the examples of potassium perfluorobutanesulfonate in the sulfonate have better overall performance.
  • Table 2 The proportions (parts by weight) and performance test results of the polycarbonate compositions of Examples 7-12
  • boehmite is not as good as mica and talc in reducing smoke density and heat release rate, but it maintains good toughness, and its comprehensive properties are more suitable for preparing polymers with a good application range. Carbonate composition products.

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Abstract

本发明提供了一种聚碳酸酯组合物，按重量份计，包括以下组分：聚碳酸酯100份；勃姆石1-30份；磺酸盐0.1-1.5份；含磷化合物1-12份。具有低烟密度和低热释放速率，韧性保持好的优点。以及公开了磺酸盐和含磷化合物在降低聚碳酸酯烟密度和热释放速率的应用，按重量份计，包括以下组分：聚碳酸酯100份；磺酸盐0.1-1.5份；含磷化合物1-12份。磺酸盐和含磷化合物在聚碳酸酯中复配使用，能够有效降低烟密度和低热释放速率。

Description

聚碳酸酯组合物和磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用 技术领域
本发明涉及高分子材料技术领域，特别是涉及聚碳酸酯组合物和磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用。
背景技术
聚碳酸酯(PC)广泛适用于交通运输行业，对人员高度集中、空间相对狭小封闭的飞机机舱而言，材料一旦着火燃烧，就会大量消耗氧气、释放热量并产生有毒可燃的气体，可燃气体会进一步助燃产生更多热量，热量集中释放就会营造一个局部的高温环境，导致材料加速降解并产生更多有毒可燃气体。随着国人对出行安全问题的重视，研发出一种在燃烧时、高温受热时低烟雾密度和低热释放的产品是市场所急需的。
中国专利CN104830041A公开了一种低热释放聚碳酸酯材料，其主要组分为溴系阻燃剂、半芳香族聚酯、硅氧烷聚碳酸酯。但是该专利溴系阻燃剂，在现阶段追求环保的趋势下不被倡导，并且溴系阻燃剂产生的烟雾毒性通常很大，对于密闭空间人员逃生不利。以及该专利没有对降低烟雾效果进行讨论。
现有技术中无卤聚合物体系，侧重于通过评价阻燃等级来优化配方，但较少考察烟雾释放量，而火灾中85％的人员伤亡是由烟气造成的，因此很有必要研究聚合物体系的生烟性。由于聚合物的燃烧机理和生烟机理完全不同，并且聚合物中加入阻燃剂时，由于燃烧更不完全，通常会加剧生烟量，因此聚合物很难同时具备良好的抑烟效果和阻燃效果，为了同时解决这两个技术问题，现有的聚合物模塑材料需要在其制备过程中添加一种或多种协效剂，才能达到阻燃和抑烟效果。一般降低烟雾释放量的做法是，加入大量的矿物填料。但是，当加入了过多的矿物填料后材料的韧性会明显下降。此时，为了解决材料韧性下降的缺陷，就需要加入增韧剂，但是，增韧剂的加入会增加烟雾释放量和热释放量。因此，需要有效降低矿物填料加入量。
发明内容
本发明的目的在于提供一种聚碳酸酯组合物，具有受高温或者燃烧时烟雾低、热释放低，韧性保持好的优点。
本发明的另一目的在于，提供磺酸盐和含磷化合物在降低聚碳酸酯烟密度和 热释放速率的应用。
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，包括以下组分：
Figure PCTCN2020072285-appb-000001
所述的含磷化合物选自六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种。
其他含磷化合物与磺酸盐复配后也具有降低烟密度以及热释放速率的功能，但是六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦的效果最好，能够在较小添加量下制备出优异低烟密度和热释放速率的聚碳酸酯组合物。
相比于聚磷酸铵、磷酸三苯酯、叔丁基磷酸三苯酯、三(2,6-二甲苯基)磷酸酯、间苯二酚-双(磷酸二苯酯)、六氨基环三磷腈、六苯氨基环三磷腈、聚二(4-羧基苯氧基)磷腈等线型聚磷腈等含常用的磷系添加剂，上述的含磷化合物(六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦)对于聚碳酸酯的烟密度和热释放速率的降低最为显著，并且对于聚碳酸酯复合材料的韧性的降低较少，更有利于推广应用。六氨基环三磷腈、六苯氨基环三磷腈对聚碳酸酯机械性能影响较大，且由于含有较多含氮基团，燃烧过程中会产生较多有毒有害的氮氧化物；聚二(4-羧基苯氧基)磷腈等线型聚磷腈由于与聚碳酸酯相容性较差，而且实际降低烟密度、热释放速率的效果也不如六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]或者三苯基氧膦好。
聚碳酸酯中最常用的矿物填料为滑石粉，其也具有一定的阻燃性能。但是，为了将低烟密度、低热释放速率的聚碳酸酯组合物推广应用，就必须要保持良好的韧性，因此，对于矿物填料的选择就不仅对低烟密度、低热释放速率进行考量，还需要得到良好的韧性保持。本发明发现，勃姆石的加入，韧性与烟密度、热释放速率的平衡较好，有利于制备得到良好综合性能的聚碳酸酯组合物。
聚碳酸酯树脂：本发明的聚碳酸酯树脂可为由二羟基化合物或其和少量的多羟基化合物与光气(phosgene)或碳酸二酯的反应获得的支化热塑性聚合物或共聚物。不特别限制聚碳酸酯树脂的生产方法，并且可使用由迄今为止已知的光气法(界面聚合法)或熔融法(酯交换法)生产的聚碳酸酯树脂。优选芳族二羟基化合物为原料二羟基化合物，且可示例为2,2-双(4-羟苯基)丙烷(＝双酚A)、四甲基双酚A、双(4-羟苯基)-对-二异丙基苯、对苯二酚、间苯二酚、4,4-二羟基二苯等，其中优选双酚A。还可使用其中至少一个四烷基磺酸膦(tetraalkylphosphonium sulfonate)结合至前述芳族二羟基化合物的化合物。
前述中，聚碳酸酯树脂优选源于2,2-双(4-羟苯基)丙烷的芳族聚碳酸酯树脂，或源于2,2-双(4-羟苯基)丙烷和其它芳族二羟基化合物的芳族聚碳酸酯共聚物。聚碳酸酯树脂还可是其中主要组成为芳族聚碳酸酯树脂的共聚物，例如，与含硅氧烷结构的聚合物或低聚物的共聚物。此外，可使用两种或更多种的上述聚碳酸酯树脂的混合物。一元芳族羟基化合物可用于调整聚碳酸酯树脂的分子量，例如，间甲基苯酚、对甲基苯酚、间丙基苯酚、对丙基苯酚、对叔丁基苯酚和对-(长链烷基)-取代酚。
本发明对聚碳酸酯树脂的生产方法没有特别限制，且可使用由光气法(界面聚合法)或熔融法(酯交换法)生产的聚碳酸酯树脂。聚碳酸酯树脂还通过由熔融法生产的聚碳酸酯树脂进行调节末端羟基的量的后处理来提供。
所述的磺酸盐选自全氟乙烷磺酸四乙基铵、二苯砜磺酸钾、全氟烷基磺酸钾、苯磺酰基苯磺酰钾、对甲苯磺酸钠中的至少一种；
优选的，所述的磺酸盐选自全氟丁基磺酸钾。
所述的含磷化合物选自六苯氧环三磷腈、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]中的至少一种；所述的勃姆石的粒径为0.1微米-13微米。进一步的，所述矿物填料的粒径为0.1微米-13微米。
当矿物填料的粒径小于0.1微米，其表面积太大，在同样的加入量下对聚碳酸酯的降解作用大幅提高，并且因为粒径太小，容易聚团，给加工带来困难；当矿物填料粒径大于13微米时，力学性能不足。生产、试验过程所用的填料的粒径一般是分布在一定范围内的，比如4-6微米，或者更宽的3-7微米的范围。
为了增加组合物燃烧时或者受高温时的抗滴落性能，按重量份计，还包括 0-5重量份的抗滴落剂；所述的抗滴落剂选自聚四氟乙烯、硅酮包覆的聚四氟乙烯、甲基丙烯酸酯聚合物包覆的聚四氟乙烯、苯乙烯-丙烯腈共聚物包覆聚四氟乙烯中的至少一种。
按照聚碳酸酯组合物的其他性能需求，还可以包括0-10重量份的助剂；所述助剂为热稳定剂、抗氧剂、光稳定剂、增塑剂、填料和着色剂中的至少一种。
所述润滑剂为硬脂酸金属盐类润滑剂、硬脂酸烷基酯类润滑剂、硬脂酸季戊四醇酯类润滑剂、石蜡或褐煤蜡。
所述热稳定剂为有机亚磷酸酯，优选为亚磷酸三苯酯、亚磷酸三-(2,6-二甲基苯基)酯、亚磷酸三-壬基苯基酯、二甲基苯膦酸酯或磷酸三甲酯。
所述抗氧剂为有机亚磷酸酯、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、苄基化合物或多元醇酯类抗氧剂。
所述光稳定剂为苯并三唑类光稳定剂或二苯甲酮类光稳定剂中的至少一种。
所述增塑剂为邻苯二甲酸酯。
所述着色剂为颜料或染料。
上述的聚碳酸酯组合物的制备方法，包括以下步骤：按配比称量聚碳酸酯、磺酸盐、含磷化合物、勃姆石、助剂，然后在高速混料机中混合均匀，然后投入双螺杆挤出机中挤出造粒得到聚碳酸酯组合物。
磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用，按重量份计，包括以下组分：
聚碳酸酯              100份；
磺酸盐                0.1-1.5份；
含磷化合物            1-12份。
优选的，按重量份计，包括以下组分：
聚碳酸酯              100份；
磺酸盐                0.2-0.8份；
含磷化合物            2-10份。
含磷化合物的用量可以是2份、3份、4份、至12份的任意份数。
随着磺酸盐的用量上升，烟释放和热释速率的变化为先降低后上升，在优选 的范围内，烟释放密度及热释放速率综合控制的较好，并且，韧性的衰减也较少。但是，磺酸盐的加入量过大也会引起组合物的韧性降低。
所述的磺酸盐选自全氟乙烷磺酸四乙基铵、二苯砜磺酸钾、全氟烷基磺酸钾、苯磺酰基苯磺酰钾、对甲苯磺酸钠中的至少一种；
优选的，所述的磺酸盐选自全氟丁基磺酸钾。
所述含磷化合物可以是六苯氧环三磷腈、磷酸三苯酯、间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种。
优选的，所述的含磷化合物选自六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种。
按重量份计，还包括0-30份矿物填料；所述的矿物填料选自滑石粉、钛白粉、云母、硫化锌、碳酸钙、硫酸钡、硫酸镁、氢氧化镁、氮化硼、蒙脱土、高岭土、勃姆石、硼酸锌中的至少一种；
优选的，所述的矿物填料选自云母、硼酸锌中的至少一种；在降低烟密度和热释放速率方面，云母、硼酸锌效果最好。
所述矿物填料的粒径为0.1微米-13微米。
本发明具有如下有益效果
本发明发现，磺酸盐和含磷化合物的复配还能够有效降低聚碳酸酯组合物的烟雾释放密度和热释放速率，在制备低烟、低热释放的聚碳酸酯组合物的应用中，能够有效降低矿物填料的用量，因此材料的韧性也得到良好的保持。
具体实施方式
本发明通过以下实施例来进一步说明本发明，但是本发明不受以下实施例限制。
本发明所用原料均来源于市售产品。
磺酸盐A：全氟丁基磺酸钾；
磺酸盐B：苯磺酰基苯磺酰钾；
含磷化合物A：间苯二酚双[二(2,6-二甲基苯基磷酸酯)]；
含磷化合物B：双酚A-双(磷酸二苯酯)；
勃姆石：粒径4-6微米；
滑石粉：粒径4-6微米；
云母：粒径4-6微米；
硼酸锌：粒径4-6微米；
抗滴落剂：苯乙烯-丙烯腈共聚物包覆聚四氟乙烯；
润滑剂：LOXIOL P 861/3.5；
抗氧剂：CHINOX 10766；
实施例和对比例聚碳酸酯组合物的制备方法：按配比称量聚碳酸酯、磺酸盐、含磷化合物、矿物填料、抗滴落剂，在高速混料机中混合均匀，然后投入双螺杆挤出机中挤出造粒得到聚碳酸酯组合物。
各项性能测试方法
(1)缺口冲击强度：测试标准ASTM D256。
(2)烟密度：测试标准ISO 5659，测试条件为50kw，无焰，对比4分钟时的烟密度(Ds(4))，数值越小越好。
(3)热释放速率：测试标准为ISO 5660，测试条件为50kw，最大平均热释放速率(MARHE)，数值越小越好。
表1：实施例1-6和对比例1-3聚碳酸酯组合物的配比(重量份)及各项性能测试结果
Figure PCTCN2020072285-appb-000002
从对比例3可以看出，加入大量滑石粉代替磺酸盐也可以降低一些烟密度和热释放速率，但是缺口冲击强度会大幅下降。
从对比例1/2可以看出，单独加入磺酸盐或者含磷化合物都不具备烟密度和热释放速率同时降低的功能。
从实施例3/5可以看出，磺酸盐中全氟丁基磺酸钾的实施例综合性能较好。表2：实施例7-12聚碳酸酯组合物的配比(重量份)及各项性能测试结果
Figure PCTCN2020072285-appb-000003
从实施例9-12可以看出，勃姆石对于烟密度和热释放速率的降低不如云母和滑石粉，但是其对于韧性的保持很好，其综合性能更适于制备出良好应用范围的聚碳酸酯组合物产品。

Claims (10)

  1. 一种聚碳酸酯组合物，其特征在于，按重量份计，包括以下组分：
    Figure PCTCN2020072285-appb-100001
    所述的含磷化合物选自六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种。
  2. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述的磺酸盐选自全氟乙烷磺酸四乙基铵、二苯砜磺酸钾、全氟烷基磺酸钾、苯磺酰基苯磺酰钾、对甲苯磺酸钠中的至少一种；优选的，所述的磺酸盐选自全氟丁基磺酸钾。
  3. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述的含磷化合物选自六苯氧环三磷腈、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]中的至少一种。
  4. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，所述的勃姆石的粒径为0.1微米-13微米。
  5. 根据权利要求1所述的聚碳酸酯组合物，其特征在于，按重量份计，还包括0-5重量份的抗滴落剂；所述的抗滴落剂选自聚四氟乙烯、硅酮包覆的聚四氟乙烯、甲基丙烯酸酯聚合物包覆的聚四氟乙烯、苯乙烯-丙烯腈共聚物包覆聚四氟乙烯中的至少一种。
  6. 磺酸盐和含磷化合物在降低聚碳酸酯发烟和热释放的应用，其特征在于，按重量份计，包括以下组分：
    聚碳酸酯               100份；
    磺酸盐                 0.1-1.5份；
    含磷化合物             1-12份。
  7. 根据权利要求6所述的应用，其特征在于，按重量份计，包括以下组分：
    聚碳酸酯               100份；
    磺酸盐                 0.2-0.8份；
    含磷化合物             2-10份。
  8. 根据权利要求6或7所述的应用，其特征在于，所述的磺酸盐选自全氟乙烷磺酸四乙基铵、二苯砜磺酸钾、全氟烷基磺酸钾、苯磺酰基苯磺酰钾、对甲苯磺酸 钠中的至少一种；优选的，所述的磺酸盐选自全氟丁基磺酸钾。
  9. 根据权利要求6或7所述的应用，其特征在于，所述含磷化合物选自六苯氧环三磷腈、磷酸三苯酯、间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种；优选的，所述的含磷化合物选自六苯氧环三磷腈、双酚A-双(磷酸二苯酯)、间苯二酚双[二(2,6-二甲基苯基磷酸酯)]、三苯基氧膦中的至少一种。
  10. 根据权利要求6或7所述的应用，其特征在于，按重量份计，还包括0-30份矿物填料；所述的矿物填料选自滑石粉、钛白粉、云母、硫化锌、碳酸钙、硫酸钡、硫酸镁、氢氧化镁、氮化硼、蒙脱土、高岭土、勃姆石、硼酸锌中的至少一种；优选的，所述的矿物填料选自云母、硼酸锌中的至少一种；所述矿物填料的粒径为0.1微米-13微米。
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