WO2021143348A1 - 一种pps组合物及其制备方法 - Google Patents

一种pps组合物及其制备方法 Download PDF

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WO2021143348A1
WO2021143348A1 PCT/CN2020/130132 CN2020130132W WO2021143348A1 WO 2021143348 A1 WO2021143348 A1 WO 2021143348A1 CN 2020130132 W CN2020130132 W CN 2020130132W WO 2021143348 A1 WO2021143348 A1 WO 2021143348A1
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pps
chlorine
chloride
pps composition
ethylene
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PCT/CN2020/130132
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English (en)
French (fr)
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王文超
黄险波
叶南飚
吴小漫
禹权
丁超
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金发科技股份有限公司
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Publication of WO2021143348A1 publication Critical patent/WO2021143348A1/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
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • 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
    • C08K3/16—Halogen-containing compounds
    • C08K2003/168—Zinc halides

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a PPS composition and a preparation method thereof.
  • Polyphenylene sulfide has excellent heat resistance, solvent resistance, high dimensional stability, and also has excellent dielectric properties, excellent flame retardancy and mechanical properties, and is widely used in electronics, automobiles, machinery, and chemicals And other fields. Because PPS has excellent fluidity and wettability, it is especially suitable for high-filled products. Moreover, because the reinforced and filled PPS has a metal-like sound, it is suitable for injection molding products with metal texture.
  • the high reactivity of the acid anhydride functional group determines that it can form a stable chemical bond with the T treatment agent dried and retained in the metal surface nanopores at the moment of integrated injection molding. This process further enhances the bonding of the PPS resin and the metal material contact interface force.
  • the focus of the above two patents is the wettability of the metal insert and the resin material, and the added elastomer has insufficient toughening effect.
  • the wettability of metal particles in the resin matrix can be known from the density and mechanical properties of the PPS composition.
  • Chinese patent 2018109351961 discloses a PPS composition that changes the content of chlorine in the PPS composition by adding a certain amount of chlorine-containing compounds to improve the mechanical properties of the glass fiber reinforced PPS composition.
  • glass fiber is a silicate, and its disclosed chlorine content range is only applicable to glass fiber reinforcement formulations, and cannot be directly used in PPS compositions filled with metal particles.
  • the purpose of the present invention is to provide a PPS composition in which special PPS is selected. Compared with other PPS, the PPS and metal powder screened by the present invention have strong wettability, thereby improving the mechanical properties and density of the PPS composition. .
  • Another object of the present invention is to provide a method for preparing the above-mentioned PPS composition.
  • a PPS composition in parts by weight, includes the following components:
  • the PPS is linear, and the chlorine content ranges from 1500 ppm to 3600 ppm based on the total weight of the PPS composition.
  • the chlorine content ranges from 2500 ppm to 3300 ppm.
  • the presence of chlorine element can enhance the wettability of PPS, strengthen the wettability with metal particles, and further improve the mechanical properties.
  • the chlorine element is derived from chlorine-containing compounds and PPS resin.
  • PPS there will be a certain amount of chlorine in the PPS resin product due to the residue of the catalyst, the introduction of chlorine in the reaction monomer, and the residue of the reaction by-products.
  • most resin manufacturers will carry out the chloride removal process after polymerization of the PPS resin, so that the residual amount of chlorine in the PPS resin is very small (based on the weight of the resin, generally 30-100ppm).
  • the present invention finds that a certain amount of chlorine contained in the PPS composition will affect the interface bonding force between the resin and the metal particle filler, thereby affecting the macroscopic properties.
  • PPS can be divided into linear and non-linear.
  • the present invention found that, from a structural point of view, linear PPS has no cross-linked structure, on the one hand, it has higher toughness, and on the other hand, it has better rheology and is easy to combine with metal particles. Tests have shown that the molecular weight range of PPS that can achieve the purpose of the present invention is 15000-100000.
  • Determination of chlorine content of chlorine element Refer to EN14582 standard for testing and use ion chromatography to test. First, the PPS composition sample is burned in an oxygen bomb, and then absorbed by sodium carbonate absorption solution, and finally the filtered absorption solution is analyzed by IC chromatograph , Determine the element type according to the peak position of the obtained chromatogram, and determine the content of chlorine element by the integrated area of the chromatographic peak.
  • the chlorine-containing compound is selected from one or more of inorganic metal chlorides, chlorine-containing organic chlorides, and chlorine-containing organic polymer compounds, and the inorganic metal chlorides are selected from sodium chloride, potassium chloride, and chlorinated compounds.
  • the inorganic metal chlorides are selected from sodium chloride, potassium chloride, and chlorinated compounds.
  • the chlorine-containing organic chloride and the chlorine-containing organic polymer compound are selected from polychlorinated naphthalenes
  • polychlorinated benzene and polychlorinated biphenyl are selected from polychlorinated naphthalenes.
  • the chlorine-containing compound is selected from one or more of sodium chloride, potassium chloride, and lithium chloride.
  • the chlorine-containing compound of the first main group is preferred, which can further improve the wettability of PPS and metal particles.
  • the metal particles are selected from at least one of iron powder, aluminum powder, copper powder, silver powder, gold powder, and zinc powder.
  • the metal powder used therein can usually be prepared by mechanical or physical and chemical methods. Due to the high density of the metal, the volume fraction in the blend is relatively low, so a large proportion can be added, but the density is too high and The addition amount will easily lead to the reduction of the mechanical strength of the strip and the broken strip, which makes it impossible to produce. Therefore, there are certain requirements for the wettability and mechanical properties of the matrix resin.
  • the resin with lower molecular weight has good wettability to metal powder, and the resin with higher molecular weight.
  • the mechanical properties of the metal powder are better.
  • the metal powders of different particle sizes will have different processing properties on the mechanical properties. Therefore, it is necessary to optimize the molecular weight of the resin and the particle size of the metal powder.
  • the particle size range of the metal particles is 100-10000 mesh.
  • the particle size of the metal particles can be measured using a laser diffraction scattering particle size distribution measuring device or a precision particle size distribution measuring device.
  • 0-20 parts by weight of a toughening agent are also included.
  • the toughening agent is selected from styrene-ethylene-butene-styrene copolymer, styrene-butene-styrene copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, epoxy At least one of ethylene-methyl acrylate copolymer, epoxidized ethylene-butyl acrylate copolymer, and ethylene octene copolymer.
  • auxiliary agents are also included.
  • the auxiliary agent is selected from at least one of antioxidants, lubricants, light stabilizers, and heat stabilizers.
  • Antioxidants include primary antioxidants or stabilizers (such as hindered phenols and/or secondary arylamines) and optional secondary antioxidants (such as phosphate esters and/or thioesters).
  • Suitable antioxidants include, for example, organic phosphates such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc., alkylated monohydric phenols or polyhydric phenols; alkylation reaction products of polyhydric phenols and dienes, such as tetra[methylene ( 3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane, etc.; butylated reaction product of p-
  • Suitable heat stabilizers include, for example, organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphites , Etc.; phosphonates, such as dimethylphenylphosphonate, etc.; phosphates, such as trimethyl phosphate, etc.; or a combination containing at least one of the foregoing heat stabilizers.
  • organic phosphites such as triphenyl phosphite, tris(2,6-dimethylphenyl) phosphite, tris(mixed mono- and dinonylphenyl) phosphites , Etc.
  • phosphonates such as dimethylphenylphosphonate, etc.
  • phosphates such as trimethyl phosphate, etc.
  • Suitable light stabilizers include, for example, benzotriazoles, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzene Triazole and 2-hydroxy-4-n-octyloxybenzophenone, etc., also include triazine-based ultraviolet light absorbers or a combination containing at least one of the foregoing light stability.
  • benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-benzene Triazole and 2-hydroxy-4-n-octyloxybenzophenone, etc.
  • triazine-based ultraviolet light absorbers or a combination containing at least one of the foregoing light stability.
  • the lubricants include, but are not limited to, pentaerythritol stearate or polyethylene wax.
  • the preparation method of the above-mentioned PPS composition includes the following steps: mix PPS and the chlorine-containing compound uniformly according to the ratio, and then add it to the twin-screw extruder, side feed the metal particles, the screw temperature is 180-290°C, and the extruder Pellets to obtain a PPS composition.
  • the tested content will be slightly reduced compared to the actual chlorine content in the chlorine-containing compound.
  • the present invention has the following beneficial effects:
  • the present invention uses linear PPS and adds a certain amount of chlorine-containing compounds to the composition to increase the content of chlorine in the PPS composition, thereby improving the wettability of PPS and metal particles, thereby improving the mechanical properties and mechanical properties of the PPS composition. density.
  • the sources of raw materials used in the present invention are as follows:
  • PPS-1 Linear PPS, chlorine content is about 45ppm, molecular weight is about 36000;
  • PPS-2 Non-linear PPS, chlorine content is 51ppm, molecular weight is about 35000;
  • Polychlorinated naphthalene analytically pure, the average chlorine element content per molecule is about 5;
  • Metal particles A iron powder, with a particle size of 800 mesh;
  • Metal particles B zinc powder, with a particle size of 800 mesh;
  • Toughening agent styrene-ethylene-butene-styrene copolymer, brand SEBS 6151;
  • Lubricant pentaerythritol stearate
  • Antioxidant hindered phenolic antioxidant
  • the preparation method of the PPS composition of the Examples and Comparative Examples According to the ratio, PPS, chlorine-containing compounds (sodium chloride, zinc chloride, dichlorobenzene), tougheners, lubricants, and antioxidants are mixed uniformly and then added to the double In the screw extruder, metal particles are fed into the side feed, the screw temperature is 180-290°C, and the PPS composition is obtained by extrusion and granulation.
  • Test method for chlorine content in PPS composition Determination of chlorine content: Ion chromatography is used to test, the PPS composition sample is first burned in an oxygen bomb, and then absorbed by sodium carbonate absorption solution, and finally the filtered absorption solution Analyze with IC chromatograph, determine the element type according to the peak position of the obtained chromatogram, and determine the content of chlorine element by the integrated area of the chromatogram peak (for the convenience of comparison, it is only reserved to ten digits).
  • Table 1 The distribution ratio (parts by weight) of each group of the PPS composition of the embodiment and the results of each performance test
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Example 7 PPS-1 100 100 100 100 100 100 100 100 100 100 100 100 Metal particles A 200 200 200 200 200 200 To Metal particles B To To To To To To To 200 Sodium chloride 0.80 1.30 1.50 1.850 To To 1.70 Zinc chloride To To To To 1.50 To To To Polychlorinated naphthalene To To To To To 1.40 To Chlorine element content, ppm 1540 2500 2880 3520 2480 2470 3240 Toughener 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Lub
  • Example 2/5/6 It can be seen from Example 2/5/6 that the type of chlorine-containing compound has little effect on the mechanical properties.
  • the main factor affecting the mechanical properties is the content of chlorine element.
  • Example 2 with a large chlorine content has better mechanical properties.
  • Example 1/2/3/4/7 It can be seen from Example 1/2/3/4/7 that the preferred chlorine element content range is 2500-3300 ppm, and the mechanical properties are better.
  • Table 2 The distribution ratio (parts by weight) of each group of the PPS composition of the comparative example and the results of each performance test
  • Comparative example 1 Comparative example 2 Comparative example 3 PPS-1 100 100 To PPS-2 To To 100 Metal particles A 200 200 200 Sodium chloride 0.60 2.2 1.30 Chlorine element content, ppm 1160 4150 2510 Toughener 20 20 20 Lubricant 0.3 0.3 0.3 Antioxidant 0.2 0.2 0.2 Tensile strength, MPa 51 50 51 Flexural strength, MPa 80 80 81 Unnotched impact strength, kJ/cm 2 twenty one twenty two 17 Density, g/cm 3 2.8 2.8 2.8 2.8 2.8 2.8

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Abstract

本发明公开了一种PPS组合物，按重量份计，包括以下组分：PPS树脂100份；金属颗粒5-400份；所述的PPS为线性的，基于PPS组合物的总重量，氯元素含量范围是1500ppm-3600ppm，本发明通过选用线性的PPS，并且通过添加一定量的含氯化合物，使PPS组合物中的氯元素含量达到一定值，使PPS与金属颗粒的浸润性得到提升，进而提升了密度和力学性能。

Description

一种PPS组合物及其制备方法 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种PPS组合物及其制备方法。
背景技术
聚苯硫醚(PPS)具有优异的耐热性、耐溶剂、高尺寸稳定性，还具有优良的介电性能、优良的阻燃性及力学性能，广泛应用于电子电气、汽车、机械、化工等领域。由于PPS具有极佳的流动性及浸润性，特别适合用来做高填充产品，而且，由于增强及填充PPS具有类似金属的声音，适合用来注塑金属质感的产品。
普通的增强及矿粉填充的PPS由于填充物的密度较低，其密度很难超过2g/cm 3。并且，由于文具、玩具及体育器材行业，对所用材料具有一定的手感及重量要求，因此利用金属填充的高密度PPS材料来制作文具、玩具及体育器材等，可以大大提高设计的自由度，提高生产效率。
但是，金属颗粒与PPS的浸润性较差，因此对于密度、力学性能的提升很有限。中国专利201510237846.1公开了酸酐改性的苯乙烯热塑性弹性体在对PPS树脂增韧的同时还可以有效改变PPS树脂体系具有高反应活性、极性和中强酸性，可以在对材料增韧的同时提高树脂的极性，改变酸碱性，进一步可增加树脂熔体高温下对金属表面的润湿性，从而增加与金属之间的粘结力。酸酐官能团的高反应活性决定它可以在一体化注塑成型的瞬间可能和金属表面纳米孔洞中干燥保留下来的T处理剂形成稳定的化学键，该过程进一步增强了PPS树脂与金属材料接触界面的粘结力。但是，上述两件专利的着重点是金属嵌件与树脂材料的浸润性，并且其加入的弹性体增韧效果不足。金属颗粒在树脂基体中的浸润性可以根据PPS组合物的密度、力学性能得知。
中国专利2018109351961公开了一种PPS组合物，通过加入一定量的含氯化合物来改变PPS组合物中氯元素的含量，以提高玻纤增强PPS组合物的力学性能。但是，玻璃纤维是一种硅酸盐，其公开的氯元素含量范围，仅适用于玻纤的增强配方，不能直接用在金属颗粒填充的PPS组合物中。
发明内容
本发明的目的在于，提供一种PPS组合物，其中特选特殊的PPS，相比于其他PPS，本发明筛选出的PPS和金属粉末浸润性强，进而提高了PPS组合物的力学性能与密度。
本发明的另一目的在于，提供上述PPS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PPS组合物，按重量份计，包括以下组分：
PPS树脂           100份；
金属颗粒          5-400份；
所述的PPS为线性的，基于PPS组合物的总重量，氯元素含量范围是1500ppm-3600ppm。
优选的，基于PPS组合物的总重量，氯元素含量范围是2500ppm-3300ppm。
在优选的范围内，氯元素的存在能够增强PPS的浸润性，与金属颗粒的浸润性更强，更进一步提升了力学性能。
所述的氯元素来源于含氯化合物以及PPS树脂。PPS中，会因催化剂的残留、反应单体中氯元素的带入，以及反应副产物的残留而使PPS树脂产品中含有一定量的氯元素。一般的，现阶段大部分树脂生产厂商都会对PPS树脂聚合后进行除氯化物工艺，使出厂的PPS树脂中氯元素残留量很小(基于树脂的重量，一般30-100ppm)。本发明发现，PPS组合物中含有一定量的氯元素会影响树脂与金属颗粒填充物之间的界面结合力，进而影响宏观性能。
PPS可以分为线性的、非线性的。本发明发现，从结构上看，线性PPS由于没有交联结构，一方面其韧性较高，另一方面会具有较好的流变性，易于与金属颗粒结合。试验表明，能够实现本发明目的PPS的分子量范围是15000-100000。
氯元素含氯测定：参照EN14582标准检测，采用离子色谱法测试，先将PPS组合物样品在氧弹中燃烧，再经碳酸钠吸收液吸收，最后将过滤后的吸收液用IC色谱仪进行分析，根据所得到的色谱图峰位置判定元素种类，色谱峰积分面积确定氯元素的含量。
所述含氯化合物选自无机金属氯化物、含氯有机氯化物以及含氯有机高分子化合物中的一种或几种，所述无机金属氯化物选自氯化钠、氯化钾、氯化锂、氯化镁、氯化铝、氯化钙、氯化铁、氯化铜或氯化锌中的一种或几种；所述含氯有机氯化物以及含氯有机高分子化合物选自多氯萘、多氯代苯、多氯代联苯中的一种或几种。
优选的，含氯化合物选自氯化钠、氯化钾、氯化锂中的一种或多种。本发明优选第一主族的含氯化合物，能够进一步提高PPS与金属颗粒的浸润性。
所述的金属颗粒选自铁粉、铝粉、铜粉、银粉、金粉、锌粉中的至少一种。其中所用金属粉末通常可用机械法或者物理化学法制备，由于金属的密度较高，使其在共混物中所占的体积份数较低，因此可以添加较大比例，但是过高的密度及添加量容易导致料条力学强度降低产生断条，使得无法生产，因此对基体树脂的浸润性和力学性能有一定的要求，分子量较低的树脂对金属粉末的浸润性好，分子量较高的树脂的力学性能较好，另外，不同粒径的金 属粉末对力学性能也会有不同的加工性能，因此需要对树脂的分子量和金属粉粒径进行优选。
所述的金属颗粒的粒径范围是100-10000目。
金属颗粒的粒径可以使用激光衍射散射粒度分布测定装置或精密粒度分布测定装置进行测定。
为了增加PPS组合物的韧性，按重量份计，还包括0-20份增韧剂。
所述的增韧剂选自苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-丁烯-苯乙烯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-丙烯酸甲酯共聚物、环氧化乙烯-丙烯酸甲酯共聚物、环氧化乙烯-丙烯酸丁酯共聚物、乙烯辛烯共聚物中的至少一种。
按重量份计，还包括0-10份的助剂。
所说的助剂选自抗氧剂、润滑剂、光稳定剂、热稳定剂中的至少一种。
抗氧剂包括主抗氧剂或稳定剂(如受阻酚和/或仲芳基胺)和任选的辅助抗氧化剂(例如磷酸酯和/或硫酯)。合适的抗氧剂包括例如有机磷酸酯，例如亚磷酸三(壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等等，烷基化的一元酚或多元酚；多元酚与二烯的烷基化反应产物，例如四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸酯)]甲烷等等；对甲酚或二环戊二烯的丁基化反应产物；烷基化氢醌；羟基化硫代二苯醚；烷叉双酚；苄基化合物；β-(3,5-二叔丁基-4-羟基苯基)-丙酸与一元醇或多元醇的酯；β-(5-叔丁基-4-羟基-3-甲基苯基)-丙酸与一元醇或多元醇的酯；硫烷基或硫芳基化合物的酯，例如二硬脂基硫代丙酸酯、二月桂基硫代丙酸酯、二(十三烷基)硫代丙酸酯、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯等等；β-(3,5-二叔丁基-4-羟基苯基)-丙酸的酰胺等等；或者包含至少一种前述抗氧化剂的组合。
合适的热稳定剂包括例如有机亚磷酸酯，例如亚磷酸三苯酯、亚磷酸三(2,6-二甲基苯基)酯、亚磷酸三(混合的单和二壬基苯基)酯，等；膦酸酯，例如二甲基苯膦酸酯等；磷酸酯，例如磷酸三甲基酯等；或者包含至少一种前述热稳定剂的组合。
合适的光稳定剂包括例如苯并三唑类，例如2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)-苯并三唑和2-羟基-4-正辛氧基二苯甲酮等等，也包括三嗪类的紫外光吸收剂或者包含至少一种前述光稳定的组合。
所述的润滑剂包括但不限于季戊四醇硬脂酸酯或聚乙烯蜡。
上述的PPS组合物的制备方法，包括以下步骤：按照配比将PPS、含氯化合物混合均匀后加入双螺杆挤出机中，侧喂加入金属颗粒，螺杆温度为180-290℃，挤出造粒，得到PPS 组合物。
通过本发明的PPS组合物中氯元素含量的检测，相比于实际投入含氯化合物中氯元素的含量，测试含量会稍微减少一些。
本发明与现有技术相比，具有如下有益效果：
本发明通过使用线性的PPS、在组合物中添加一定量的含氯化合物以提高PPS组合物中的氯元素含量，提高了PPS与金属颗粒的浸润性，因此提高了PPS组合物的力学性能与密度。
具体实施方式
本发明是通过以下实施例进行更详细描述，但是本发明不受以下实施例的限制。
本发明所使用的原料来源如下：
PPS-1：线性PPS，氯元素含量约45ppm，分子量约为36000；
PPS-2：非线性PPS，氯元素含量51ppm，分子量约为35000；
氯化钠：分析纯；
氯化锌：分析纯；
多氯萘：分析纯，每分子平均氯元子含量约为5个；
金属颗粒A：铁粉，粒径为800目；
金属颗粒B：锌粉，粒径为800目；
增韧剂：苯乙烯-乙烯-丁烯-苯乙烯共聚物，牌号为SEBS 6151；
润滑剂：季戊四醇硬脂酸酯；
抗氧剂：受阻酚类抗氧剂；
实施例和对比例PPS组合物的制备方法：按照配比将PPS、含氯化合物(氯化钠、氯化锌、二氯苯)、增韧剂、润滑剂、抗氧剂混合均匀后加入双螺杆挤出机中，侧喂加入金属颗粒，螺杆温度为180-290℃，挤出造粒，得到PPS组合物。
PPS组合物中氯元素含量的测试方法：氯元素含氯测定：采用离子色谱法测试，先将PPS组合物样品在氧弹中燃烧，再经碳酸钠吸收液吸收，最后将过滤后的吸收液用IC色谱仪进行分析，根据所得到的色谱图峰位置判定元素种类，色谱峰积分面积确定氯元素的含量(为了方便比较，仅保留到十位数)。
各项性能测试方法：
  测试标准 单位
拉伸强度 ISO 527 MPa
弯曲强度 ISO178 MPa
无缺口冲击强度 ISO180 kJ/cm 2
密度 ISO 1183 g/cm 3
表1：实施例PPS组合物各组分配比(重量份)及各性能测试结果
  实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7
PPS-1 100 100 100 100 100 100 100
金属颗粒A 200 200 200 200 200 200  
金属颗粒B             200
氯化钠 0.80 1.30 1.50 1.850     1.70
氯化锌         1.50    
多氯萘           1.40  
氯元素含量，ppm 1540 2500 2880 3520 2480 2470 3240
增韧剂 20 20 20 20 20 20 20
润滑剂 0.3 0.3 0.3 0.3 0.3 0.3 0.3
抗氧剂 0.2 0.2 0.2 0.2 0.2 0.2 0.2
拉伸强度，MPa 55 59 60 56 58 58 59
弯曲强度，MPa 87 90 92 89 89 88 90
无缺口冲击强度，kJ/cm 2 21 24 24 23 24 24 23
密度，g/cm 3 2.9 2.9 2.9 2.9 2.9 2.9 2.9
从实施例2/5/6可知，含氯化合物的种类对于力学性能的影响不大，影响力学性能的因素主要是氯元素的含量，氯元素含量大的实施例2其力学性能较好。
从实施例1/2/3/4/7可知，优选的氯元素含量范围是2500-3300ppm，力学性能更好。
表2：对比例PPS组合物各组分配比(重量份)及各性能测试结果
  对比例1 对比例2 对比例3
PPS-1 100 100  
PPS-2     100
金属颗粒A 200 200 200
氯化钠 0.60 2.2 1.30
氯元素含量，ppm 1160 4150 2510
增韧剂 20 20 20
润滑剂 0.3 0.3 0.3
抗氧剂 0.2 0.2 0.2
拉伸强度，MPa 51 50 51
弯曲强度，MPa 80 80 81
无缺口冲击强度，kJ/cm 2 21 22 17
密度，g/cm 3 2.8 2.8 2.8
由上表的测试结果可知，测试得到的氯元素的含量会相对于实际加入量相近，需要根据实际测试得到的氯元素含量来评价组合物的性能。
从对比例1-2可知，氯元素含量低过低或过高，都会影响PPS组合物的力学性能。
从对比例3可知，非线性PPS作为树脂基体，其中加入含氯化合物，对于力学性能的提升不足。

Claims (10)

  1. 一种PPS组合物，其特征在于，按重量份计，包括以下组分：
    PPS树脂           100份；
    金属颗粒          5-400份；
    所述的PPS为线性的，基于PPS组合物的总重量，氯元素含量范围是1500ppm-3600ppm。
  2. 根据权利要求1所述的PPS组合物，其特征在于，基于PPS组合物的总重量，氯元素含量范围是2500ppm-3300ppm。
  3. 根据权利要求1或2所述的PPS组合物，其特征在于，所述的氯元素来源于含氯化合物以及PPS树脂。
  4. 根据权利要求1或2所述的PPS组合物，其特征在于，氯元素含氯测定：参照EN14582标准检测，采用离子色谱法测试，先将PPS组合物样品在氧弹中燃烧，再经碳酸钠吸收液吸收，最后将过滤后的吸收液用IC色谱仪进行分析，根据所得到的色谱图峰位置判定元素种类，色谱峰积分面积确定氯元素的含量。
  5. 根据权利要求3所述的PPS组合物，其特征在于，所述含氯化合物选自无机金属氯化物、含氯有机氯化物以及含氯有机高分子化合物中的一种或几种，所述无机金属氯化物选自氯化钠、氯化钾、氯化锂、氯化镁、氯化铝、氯化钙、氯化铁、氯化铜或氯化锌中的一种或几种；所述含氯有机氯化物以及含氯有机高分子化合物选自多氯萘、多氯代苯、多氯代联苯中的一种或几种；优选的，含氯化合物选自氯化钠、氯化钾、氯化锂中的一种或多种。
  6. 根据权利要求1或2所述的PPS组合物，其特征在于，所述的金属颗粒选自铁粉、铝粉、铜粉、银粉、金粉、锌粉中的至少一种。
  7. 根据权利要求6所述的PPS组合物，其特征在于，所述的金属颗粒的粒径范围是100-10000目。
  8. 根据权利要求1或2所述的PPS组合物，其特征在于，按重量份计，还包括0-20份增韧剂；所述的增韧剂选自苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-丁烯-苯乙烯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-丙烯酸甲酯共聚物、环氧化乙烯-丙烯酸甲酯共聚物、环氧化乙烯-丙烯酸丁酯共聚物、乙烯辛烯共聚物中的至少一种。
  9. 根据权利要求1或2所述的PPS组合物，其特征在于，按重量份计，还包括0-10份的助剂；所述的助剂选自抗氧剂、润滑剂、光稳定剂、热稳定剂中的至少一种。
  10. 权利要求3所述的PPS组合物的制备方法，其特征在于，包括以下步骤：按照配比将PPS、含氯化合物混合均匀后加入双螺杆挤出机中，侧喂加入金属颗粒，螺杆温度为180-290℃，挤出造粒，得到PPS组合物。
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