WO2022242289A1 - Antistatic masterbatch, preparation method therefor and use thereof - Google Patents

Antistatic masterbatch, preparation method therefor and use thereof Download PDF

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WO2022242289A1
WO2022242289A1 PCT/CN2022/081587 CN2022081587W WO2022242289A1 WO 2022242289 A1 WO2022242289 A1 WO 2022242289A1 CN 2022081587 W CN2022081587 W CN 2022081587W WO 2022242289 A1 WO2022242289 A1 WO 2022242289A1
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antistatic
resin
wax
antistatic masterbatch
parts
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PCT/CN2022/081587
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French (fr)
Chinese (zh)
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王培涛
陈平绪
叶南飚
岑茵
艾军伟
丁超
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金发科技股份有限公司
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02Polyalkylene oxides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12Polyester-amides
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02Acrylonitrile-Butadiene-Styrene [ABS] polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
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    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04Homopolymers or copolymers of ethene
    • C08J2423/08Copolymers of ethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00Characterised by the use 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; Derivatives of such polymers
    • C08J2425/02Homopolymers or copolymers of hydrocarbons
    • C08J2425/04Homopolymers or copolymers of styrene
    • C08J2425/08Copolymers of styrene
    • C08J2425/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/017Additives being an antistatic agent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/04Antistatic

Definitions

  • the invention relates to the technical field of polymer materials, in particular to an antistatic masterbatch and its preparation method and application.
  • the antistatic technology of polycarbonate is mainly realized by adding antistatic agents.
  • the direct addition of antistatic agents has the defects of uneven dispersion and difficult processing; on the other hand, antistatic agents need to be concentrated on the surface of the workpiece to form a sufficiently uniform and dense conductive network.
  • the traditional antistatic masterbatch can improve the dispersion performance to a certain extent, but it cannot solve the problem of differences in different positions of the same part. If the method of increasing the content of the antistatic agent will cause local uneven dispersion, increase the risk of electrical breakdown, and affect the mechanical properties.
  • the object of the present invention is to provide an antistatic masterbatch, which can achieve uniform antistatic surface resistance and maintain good mechanical properties when applied to ABS/PC alloys.
  • a kind of antistatic masterbatch, by weight, comprises following components:
  • the carboxylic ionomer is an ethylene/methacrylic acid copolymer, wherein 25mol%-90mol% of the carboxyl groups in the methacrylic acid unit are neutralized by metal ions; preferably, 40mol% of the methacrylic acid unit -80 mol% of carboxyl groups are neutralized by metal ions.
  • the amount of carboxyl group neutralized by metal ions can be calculated according to the characteristic absorption peak area of carboxylate after acid-base titration or Fourier transform infrared detector test.
  • the metal ion is at least one selected from sodium ion, zinc ion, magnesium ion and potassium ion, the melt index of the carboxylic acid-based ionomer is between 0.5-6g/10min, and the test condition is 190°C , 2.16kg.
  • the content of AN in the AS resin is 18-36wt%; preferably, the content of AN in the AS resin is 25-28wt%.
  • AS resin is a styrene-acrylonitrile copolymer, and the characteristics of AS resin can be adjusted by adjusting the content of styrene monomer (S) and acrylonitrile monomer (AN).
  • S styrene monomer
  • AN acrylonitrile monomer
  • the invention selects AS resins with different AN contents to improve the uniform dispersion of the antistatic agent in the PC/ABS alloy resin matrix.
  • the antistatic agent is selected from the group consisting of ethoxylated alkylamine, ethoxylated lauryl amide, glyceric acid ester, higher alcohol sulfate ester salt, polyethylene oxide, polyether ester amide, polyether ester imide At least one of; Preferably, the antistatic agent is selected from at least one of polyethylene oxide and polyether ester amide.
  • the wax polymer is selected from one or more of polyethylene wax, oxidized polyethylene wax, maleic anhydride modified polyethylene wax, and low molecular weight copolyamide wax; preferably, the wax polymer At least one selected from oxidized polyethylene wax and maleic anhydride modified polyethylene wax.
  • auxiliary agents are also included; said auxiliary agents are selected from at least one of antioxidants and lubricants.
  • the preparation method of the antistatic masterbatch of the present invention comprises the following steps: according to the proportion, the carboxylic acid-based ionomer, AS resin, antistatic agent and wax polymer are uniformly mixed and then extruded by a twin-screw extruder to produce pellets, the screw temperature is 200-270°C, and the speed range is 180-500r/min.
  • antistatic masterbatch of the present invention is used to prepare antistatic PC/ABS alloy, and comprises the following components in parts by weight:
  • the antistatic masterbatch of the present invention is not particularly limited to PC resin and ABS resin.
  • the present invention provides an antistatic masterbatch.
  • the dispersion in the polymer is good.
  • the addition of AS resin can improve the compatibility of the carboxylic acid-based ionomer and ABS, making it tend to the ABS resin.
  • the third, carboxylic acid-based ionomer has certain compatibility with PC resin and tends to disperse on the surface of PC resin, so that the antistatic masterbatch of the present invention can make the antistatic agent in PC/ABS alloy
  • the PC/ABS alloy has uniform and high-density dispersion on the surface, and at the same time forms a uniform antistatic network inside, which solves the problem of surface resistivity differences caused by dispersion at different positions of the alloy, and can maintain good mechanical properties at the same time.
  • the raw material sources used in the present invention are as follows:
  • PC resin brand PC S-2000F, weight average molecular weight 22000-25000.
  • ABS resin grade is ABS 8391
  • AN content is 26.5wt%, grade SAN NF2200AK;
  • AS resin B AN content is 19.5wt%, grade SAN 310N TR;
  • AS resin C AN content is 35wt%, grade SAN 350N;
  • AS resin D AN content is 17wt%, grade SAN 310TR;
  • Carboxylic acid-based ionomer A the main chain is ethylene/methacrylic acid copolymer, the melt index is 3.5g/10min, the test conditions are 190°C, 2.16kg, and 78mol% of the carboxyl groups of the methacrylic acid unit are neutralized by sodium ions.
  • Carboxylic acid-based ionomer B the main chain is ethylene/methacrylic acid copolymer, the melt index is 1.4g/10min, the test conditions are 190°C, 2.16kg, and 45mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
  • Carboxylic acid-based ionomer C The main chain is ethylene/methacrylic acid copolymer, the melt index is 5.9g/10min, the test conditions are 190°C, 2.16kg, and 26mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
  • Carboxylic acid-based ionomer D the main chain is ethylene/methacrylic acid copolymer, the melt index is 4.0g/10min, the test conditions are 190°C, 2.16kg, and 86mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
  • Antistatic agent A polyethylene oxide, manufacturer Sanyo Chemical industries
  • Antistatic agent B polyether ester amide, manufacturer IonPhasE;
  • Antistatic agent C Ethoxylauramide, manufacturer Adeka;
  • Wax polymer A oxidized polyethylene wax, manufactured by Honeywell;
  • Wax polymer B maleic anhydride modified polyethylene wax, Mitsui Chemicals;
  • Wax polymer C low molecular weight copolyamide wax, SUNMIDE 50, manufacturer Evonik;
  • the preparation method of A series and B series antistatic masterbatch According to the proportion, mix carboxylic acid ionomer, AS resin, antistatic agent and wax polymer evenly, and then extrude and granulate through twin-screw extruder.
  • the screw temperature is 200-270°C, and the speed range is 180-500r/min.
  • PC resin PC resin
  • ABS resin ABS resin
  • antistatic masterbatch or antistatic agent
  • extrude granulation by twin-screw extruder screw speed is 180-450r /min, the temperature range is 200-270°C
  • Table 1 Distribution ratio of each component of A 1-4 antistatic masterbatch (parts by weight)
  • Table 2 Distribution ratio of each component of A 5-9 antistatic masterbatch (parts by weight)
  • Table 3 Distribution ratio of each component of A 10-15 antistatic masterbatch (parts by weight)
  • Table 4 Distribution ratio of each component of B antistatic masterbatch (parts by weight)
  • Table 5 The distribution ratio (parts by weight) and test results of each component of the PC/ABS alloy of the embodiment and the comparative example
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 PC resin 50 50 50 50 50 50
  • Antistatic masterbatch types A1 A2 A3 A4 A5 Antistatic masterbatch, dosage 30 30 30 30 30 antistatic agent - - - - - - Surface Resistance - Front ⁇ 10 ⁇ 9 10 ⁇ 9 10 ⁇ 8 10 ⁇ 9 10 ⁇ 8 Surface resistance - reverse side ⁇ 10 ⁇ 9 10 ⁇ 9 10 ⁇ 10 10 ⁇ 9 Izod notched impact strength kJ/m 2 40 36 33 35 41
  • Example 6 Example 7
  • Example 8 Example 9 PC resin 50 50 50 50 50 ABS resin 50 50 50 50 50 Antistatic masterbatch, types A6 A7 A8 A9 Antistatic masterbatch, dosage 30 30 30 30 antistatic agent - - - - Surface Resistance - Front ⁇ 10 ⁇ 10 10 ⁇ 8 10 ⁇ 10 10 ⁇ 9 Surface resistance - reverse side ⁇ 10 ⁇ 11 10 ⁇ 9 10 ⁇ 10 10 ⁇ 10 Izod notched impact strength kJ/m 2 34 38 43 39
  • the AS resin preferably has an AN content of 25-28 wt%, and the resistance value of the front and back surfaces is more stable.
  • the antistatic agent is preferably polyethylene oxide or polyether ester amide, not only the front and back resistance values are more stable, but also the Izod notched impact strength is better.
  • the waxy polymer is preferably oxidized polyethylene wax, maleic anhydride modified polyethylene wax, although the notched Izod impact strength value of Example 9 using low molecular weight copolyamide wax is higher, but Oxidized polyethylene wax and maleic anhydride modified polyethylene wax have better resistance dispersion uniformity.
  • Comparative Example 1 It can be seen from Comparative Example 1 that the antistatic masterbatch without carboxylic acid-based ionomer has a large difference in resistance value between the front and back sides, and the resistance value is relatively low.

Abstract

Disclosed in the present invention is an antistatic masterbatch. The antistatic masterbatch comprises the following components, in parts by weight: 20-50 parts of a carboxylic-acid-based ionomer; 10-45 parts of an AS resin; 20-60 parts of an antistatic agent; and 2-8 parts of a wax polymer. The antistatic masterbatch of the present invention is applied to an ABS/PC alloy, such that a uniform antistatic surface resistance can be achieved and good mechanical properties are maintained.

Description

一种抗静电母粒及其制备方法和应用A kind of antistatic masterbatch and its preparation method and application 技术领域technical field
本发明涉及高分子材料技术领域,特别是涉及一种抗静电母粒及其制备方法和应用。The invention relates to the technical field of polymer materials, in particular to an antistatic masterbatch and its preparation method and application.
背景技术Background technique
聚碳酸酯的抗静电技术主要通过添加抗静电剂来实现。但是,一方面,抗静电剂直接添加存在分散不均、难加工的缺陷,另一方面,抗静电剂需要富集在制件的表面才能够形成足够均匀、密集的导电网络。传统的抗静电母粒能够一定程度改善分散性能,但是没法解决同一制件不同位置差异的问题。如果通过增加抗静电剂含量的方法又会造成局部分散不均,增加电击穿的风险,并且影响力学性能。The antistatic technology of polycarbonate is mainly realized by adding antistatic agents. However, on the one hand, the direct addition of antistatic agents has the defects of uneven dispersion and difficult processing; on the other hand, antistatic agents need to be concentrated on the surface of the workpiece to form a sufficiently uniform and dense conductive network. The traditional antistatic masterbatch can improve the dispersion performance to a certain extent, but it cannot solve the problem of differences in different positions of the same part. If the method of increasing the content of the antistatic agent will cause local uneven dispersion, increase the risk of electrical breakdown, and affect the mechanical properties.
进一步的,PC/ABS合金材料多为多相体系,抗静电剂在不同组分中具有选择分散的特性,因此现有技术难以将抗静电剂均匀的分散在PC/ABS合金的基体中。Furthermore, most PC/ABS alloy materials are multi-phase systems, and the antistatic agent has the characteristic of selective dispersion in different components, so it is difficult to uniformly disperse the antistatic agent in the PC/ABS alloy matrix in the prior art.
发明内容Contents of the invention
本发明的目的在于,提供一种抗静电母粒,应用于ABS/PC合金中能够实现抗静电表面电阻均匀,并且保持良好的力学性能。The object of the present invention is to provide an antistatic masterbatch, which can achieve uniform antistatic surface resistance and maintain good mechanical properties when applied to ABS/PC alloys.
本发明是通过以下技术方案实现的:The present invention is achieved through the following technical solutions:
一种抗静电母粒,按重量份计,包括以下组分:A kind of antistatic masterbatch, by weight, comprises following components:
Figure PCTCN2022081587-appb-000001
Figure PCTCN2022081587-appb-000001
优选的,按重量份计,包括以下组分:Preferably, by weight, the following components are included:
Figure PCTCN2022081587-appb-000002
Figure PCTCN2022081587-appb-000002
所述的羧酸基离聚体为乙烯/甲基丙烯酸类共聚物,其中甲基丙烯酸单元中的25mol%-90mol%的羧基被金属离子中和;优选的,甲基丙烯酸单元中的40mol%-80mol%的羧基被金属离子中和。The carboxylic ionomer is an ethylene/methacrylic acid copolymer, wherein 25mol%-90mol% of the carboxyl groups in the methacrylic acid unit are neutralized by metal ions; preferably, 40mol% of the methacrylic acid unit -80 mol% of carboxyl groups are neutralized by metal ions.
羧基被金属离子中和的量可以根据酸碱滴定或者傅里叶红外检测仪测试后根据羧酸盐的 特征吸收峰面积推算羧酸被离子中和的量。The amount of carboxyl group neutralized by metal ions can be calculated according to the characteristic absorption peak area of carboxylate after acid-base titration or Fourier transform infrared detector test.
所述的金属离子选自钠离子、锌离子、镁离子、钾离子中的至少一种,所述的羧酸基离聚体的熔融指数在0.5-6g/10min之间,测试条件为190℃、2.16kg。The metal ion is at least one selected from sodium ion, zinc ion, magnesium ion and potassium ion, the melt index of the carboxylic acid-based ionomer is between 0.5-6g/10min, and the test condition is 190°C , 2.16kg.
所述的AS树脂中AN含量为18-36wt%;优选的,AS树脂中AN含量为25-28wt%。AS树脂为苯乙烯-丙烯腈共聚物,可以通过调节苯乙烯单体(S)、丙烯腈单体(AN)的含量来调节AS树脂的特性。本发明选取不同AN含量的AS树脂,以提高抗静电剂在PC/ABS合金树脂基体中的均匀分散性。The content of AN in the AS resin is 18-36wt%; preferably, the content of AN in the AS resin is 25-28wt%. AS resin is a styrene-acrylonitrile copolymer, and the characteristics of AS resin can be adjusted by adjusting the content of styrene monomer (S) and acrylonitrile monomer (AN). The invention selects AS resins with different AN contents to improve the uniform dispersion of the antistatic agent in the PC/ABS alloy resin matrix.
所述的抗静电剂选自乙氧基化烷基胺、乙氧基月桂酰胺、甘油酸酯、高级醇硫酸酯盐、聚环氧乙烷、聚醚酯酰胺、聚醚酯酰亚胺中的至少一种;优选的,所述的抗静电剂选自聚环氧乙烷、聚醚酯酰胺中的至少一种。The antistatic agent is selected from the group consisting of ethoxylated alkylamine, ethoxylated lauryl amide, glyceric acid ester, higher alcohol sulfate ester salt, polyethylene oxide, polyether ester amide, polyether ester imide At least one of; Preferably, the antistatic agent is selected from at least one of polyethylene oxide and polyether ester amide.
所述的蜡类聚合物选自聚乙烯蜡、氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡、低分子量共聚酰胺蜡中的一种或者几种;优选的,所述的蜡类聚合物选自氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡中的至少一种。The wax polymer is selected from one or more of polyethylene wax, oxidized polyethylene wax, maleic anhydride modified polyethylene wax, and low molecular weight copolyamide wax; preferably, the wax polymer At least one selected from oxidized polyethylene wax and maleic anhydride modified polyethylene wax.
为了提升抗静电母粒得到其他性能,可以选择性的加入一定量的助剂。按重量份计,还包括0-2份助剂;所述的助剂选自抗氧剂、润滑剂中的至少一种。In order to improve the antistatic masterbatch to obtain other properties, a certain amount of additives can be selectively added. In parts by weight, 0-2 parts of auxiliary agents are also included; said auxiliary agents are selected from at least one of antioxidants and lubricants.
本发明的抗静电母粒的制备方法,包括以下步骤:按照配比,将羧酸基离聚体、AS树脂、抗静电剂、蜡类聚合物混和均匀后通过双螺杆挤出机挤出造粒,螺杆温度为200-270℃,转速范围是180-500r/min。The preparation method of the antistatic masterbatch of the present invention comprises the following steps: according to the proportion, the carboxylic acid-based ionomer, AS resin, antistatic agent and wax polymer are uniformly mixed and then extruded by a twin-screw extruder to produce pellets, the screw temperature is 200-270°C, and the speed range is 180-500r/min.
本发明的抗静电母粒的应用,用于制备抗静电PC/ABS合金,按重量份计,包括以下组分:The application of the antistatic masterbatch of the present invention is used to prepare antistatic PC/ABS alloy, and comprises the following components in parts by weight:
PC树脂         25-75份;PC resin 25-75 parts;
ABS树脂        25-75份;ABS resin 25-75 parts;
抗静电母粒     10-45份。Antistatic masterbatch 10-45 parts.
本发明的抗静电母粒对于PC树脂、ABS树脂没有特别的限制。The antistatic masterbatch of the present invention is not particularly limited to PC resin and ABS resin.
本发明具有如下有益效果:The present invention has following beneficial effect:
为了解决抗静电剂在PC/ABS的多相体系中的分散不均匀性,本发明提供了一种抗静电母粒,第一、利用了抗静电剂在羧酸离子基团的羧酸基离聚体中分散性良好,第二、由于羧酸基离聚体与ABS树脂的相容性差,因此添加AS树脂能提高羧酸基离聚体和ABS的相容性使其倾向于ABS树脂的表面,第三、羧酸基离聚体与PC树脂具有一定相容性并且更倾向于分散在PC树脂表面,使得本发明的抗静电母粒应用于PC/ABS合金后能够使得抗静电 剂在PC/ABS合金的表面均匀、高密度的分散,同时在内部形成均匀的抗静电网络,解决了合金不同位置分散导致的表面电阻率差异问题,同时能够保持良好的力学性能。In order to solve the non-uniform dispersion of antistatic agent in PC/ABS multiphase system, the present invention provides an antistatic masterbatch. The dispersion in the polymer is good. Second, because the compatibility between the carboxylic acid-based ionomer and ABS resin is poor, the addition of AS resin can improve the compatibility of the carboxylic acid-based ionomer and ABS, making it tend to the ABS resin. Surface, the third, carboxylic acid-based ionomer has certain compatibility with PC resin and tends to disperse on the surface of PC resin, so that the antistatic masterbatch of the present invention can make the antistatic agent in PC/ABS alloy The PC/ABS alloy has uniform and high-density dispersion on the surface, and at the same time forms a uniform antistatic network inside, which solves the problem of surface resistivity differences caused by dispersion at different positions of the alloy, and can maintain good mechanical properties at the same time.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
本发明所用原料来源如下:The raw material sources used in the present invention are as follows:
PC树脂:牌号PC S-2000F,重均分子量22000-25000。PC resin: brand PC S-2000F, weight average molecular weight 22000-25000.
ABS树脂:牌号为ABS 8391;ABS resin: grade is ABS 8391;
AS树脂A:AN含量为26.5wt%,牌号SAN NF2200AK;AS resin A: AN content is 26.5wt%, grade SAN NF2200AK;
AS树脂B:AN含量为19.5wt%,牌号SAN 310N TR;AS resin B: AN content is 19.5wt%, grade SAN 310N TR;
AS树脂C:AN含量为35wt%,牌号SAN 350N;AS resin C: AN content is 35wt%, grade SAN 350N;
AS树脂D:AN含量为17wt%,牌号SAN 310TR;AS resin D: AN content is 17wt%, grade SAN 310TR;
羧酸基离聚体A:主链为乙烯/甲基丙烯酸共聚物,熔融指数3.5g/10min,测试条件为190℃、2.16kg,甲基丙烯酸单元的78mol%的羧基被钠离子中和。Carboxylic acid-based ionomer A: the main chain is ethylene/methacrylic acid copolymer, the melt index is 3.5g/10min, the test conditions are 190°C, 2.16kg, and 78mol% of the carboxyl groups of the methacrylic acid unit are neutralized by sodium ions.
羧酸基离聚体B:主链为乙烯/甲基丙烯酸共聚物,熔融指数1.4g/10min,测试条件为190℃、2.16kg,甲基丙烯酸单元的45mol%的羧基被锌离子中和。Carboxylic acid-based ionomer B: the main chain is ethylene/methacrylic acid copolymer, the melt index is 1.4g/10min, the test conditions are 190°C, 2.16kg, and 45mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
羧酸基离聚体C:主链为乙烯/甲基丙烯酸共聚物,熔融指数5.9g/10min,测试条件为190℃、2.16kg,甲基丙烯酸单元的26mol%的羧基被锌离子中和。Carboxylic acid-based ionomer C: The main chain is ethylene/methacrylic acid copolymer, the melt index is 5.9g/10min, the test conditions are 190°C, 2.16kg, and 26mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
羧酸基离聚体D:主链为乙烯/甲基丙烯酸共聚物,熔融指数4.0g/10min,测试条件为190℃、2.16kg,甲基丙烯酸单元的86mol%的羧基被锌离子中和。Carboxylic acid-based ionomer D: the main chain is ethylene/methacrylic acid copolymer, the melt index is 4.0g/10min, the test conditions are 190°C, 2.16kg, and 86mol% of the carboxyl groups of the methacrylic acid unit are neutralized by zinc ions.
抗静电剂A:聚环氧乙烷,厂家Sanyo Chemical industries;Antistatic agent A: polyethylene oxide, manufacturer Sanyo Chemical industries;
抗静电剂B:聚醚酯酰胺,厂家IonPhasE;Antistatic agent B: polyether ester amide, manufacturer IonPhasE;
抗静电剂C:乙氧基月桂酰胺,厂家Adeka;Antistatic agent C: Ethoxylauramide, manufacturer Adeka;
蜡类聚合物A:氧化聚乙烯蜡,厂家Honeywell;Wax polymer A: oxidized polyethylene wax, manufactured by Honeywell;
蜡类聚合物B:马来酸酐改性聚乙烯蜡,三井化学;Wax polymer B: maleic anhydride modified polyethylene wax, Mitsui Chemicals;
蜡类聚合物C:低分子量共聚酰胺蜡,SUNMIDE 50,厂家Evonik;Wax polymer C: low molecular weight copolyamide wax, SUNMIDE 50, manufacturer Evonik;
A系列和B系列抗静电母粒的制备方法:按照配比,将羧酸基离聚体、AS树脂、抗静电剂、蜡类聚合物混和均匀后通过双螺杆挤出机挤出造粒,螺杆温度为200-270℃,转速范 围是180-500r/min。The preparation method of A series and B series antistatic masterbatch: According to the proportion, mix carboxylic acid ionomer, AS resin, antistatic agent and wax polymer evenly, and then extrude and granulate through twin-screw extruder. The screw temperature is 200-270°C, and the speed range is 180-500r/min.
实施例和对比例PC/ABS合金的制备方法:PC树脂、ABS树脂、抗静电母粒(或抗静电剂)混合均匀,再通过双螺杆挤出机挤出造粒(螺杆转速为180-450r/min,温度区间为200-270℃),得到PC/ABS合金。The preparation method of embodiment and comparative example PC/ABS alloy: PC resin, ABS resin, antistatic masterbatch (or antistatic agent) mix homogeneously, then extrude granulation by twin-screw extruder (screw speed is 180-450r /min, the temperature range is 200-270°C) to obtain PC/ABS alloy.
各项测试方法:Various test methods:
(1)悬臂梁缺口冲击强度:按照标准ISO 180进行测试,测试温度23℃。(1) Notched Izod Impact Strength: Tested according to standard ISO 180, the test temperature is 23°C.
(2)表面电阻:按照标准ASTM D257进行测试。(2) Surface resistance: Tested according to standard ASTM D257.
表1:A 1-4抗静电母粒各组分配比(重量份)Table 1: Distribution ratio of each component of A 1-4 antistatic masterbatch (parts by weight)
 the A1A1 A2A2 A3A3 A4A4
羧酸基离聚体ACarboxylate ionomer A 2020  the  the 2020
羧酸基离聚体BCarboxylate ionomer B  the 2020  the  the
羧酸基离聚体CCarboxylate ionomer C  the  the 2020  the
羧酸基离聚体DCarboxylate ionomer D  the  the  the 2020
AS树脂AAS resin A 3535 3535 3535 3535
AS树脂DAS resin D  the  the  the  the
抗静电剂AAntistatic agent A 4040 4040 4040 4040
蜡类聚合物AWax Polymer A 55 55 55 55
表2:A 5-9抗静电母粒各组分配比(重量份)Table 2: Distribution ratio of each component of A 5-9 antistatic masterbatch (parts by weight)
 the A5A5 A6A6 A7A7 A8A8 A9A9
羧酸基离聚体ACarboxylate ionomer A 2020 2020 2020 2020 2020
AS树脂AAS resin A  the  the  the 3535 3535
AS树脂BAS resin B 3535  the  the  the  the
AS树脂CAS resin C  the 3535  the  the  the
AS树脂DAS resin D  the  the 3535  the  the
抗静电剂AAntistatic agent A 4040 4040 4040  the  the
抗静电剂BAntistatic agent B  the  the  the 4040  the
抗静电剂CAntistatic agent C  the  the  the  the 4040
蜡类聚合物AWax Polymer A 55 55 55 55 55
表3:A 10-15抗静电母粒各组分配比(重量份)Table 3: Distribution ratio of each component of A 10-15 antistatic masterbatch (parts by weight)
 the A10A10 A11A11 A12A12 A13A13 A14A14 A15A15
羧酸基离聚体ACarboxylate ionomer A 2020 2020 2525 3535 4040 5050
AS树脂AAS resin A 3535 3535 3535 3030 2020 1515
抗静电剂AAntistatic agent A 4040 4040 3535 5050 3434 5555
蜡类聚合物AWax Polymer A  the  the 55 66 33 88
蜡类聚合物BWax Polymer B 55  the  the  the  the  the
蜡类聚合物CWax Polymer C  the 55  the  the  the  the
表4:B抗静电母粒各组分配比(重量份)Table 4: Distribution ratio of each component of B antistatic masterbatch (parts by weight)
 the B1B1 B2B2 B3B3 B4B4 B5B5
羧酸基离聚体ACarboxylate ionomer A  the 2020 2020 1010 7070
AS树脂AAS resin A 3535 3535  the 3535 3535
抗静电剂AAntistatic agent A 4040 4040 4040 4040 4040
蜡类聚合物AWax Polymer A 55  the 55 55 55
表5:实施例和对比例PC/ABS合金各组分配比(重量份)及测试结果Table 5: The distribution ratio (parts by weight) and test results of each component of the PC/ABS alloy of the embodiment and the comparative example
 the 实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5
PC树脂PC resin 5050 5050 5050 5050 5050
ABS树脂ABS resin 5050 5050 5050 5050 5050
抗静电母粒,种类Antistatic masterbatch, types A1A1 A2A2 A3A3 A4A4 A5A5
抗静电母粒,添加量Antistatic masterbatch, dosage 3030 3030 3030 3030 3030
抗静电剂antistatic agent -- -- -- -- --
表面电阻-正面ΩSurface Resistance - Front Ω 10^910^9 10^910^9 10^810^8 10^910^9 10^810^8
表面电阻-反面ΩSurface resistance - reverse side Ω 10^910^9 10^910^9 10^910^9 10^1010^10 10^910^9
悬臂梁缺口冲击强度kJ/m 2 Izod notched impact strength kJ/m 2 4040 3636 3333 3535 4141
续表5:Continuation of Table 5:
 the 实施例6Example 6 实施例7Example 7 实施例8Example 8 实施例9Example 9
PC树脂PC resin 5050 5050 5050 5050
ABS树脂ABS resin 5050 5050 5050 5050
抗静电母粒,种类Antistatic masterbatch, types A6A6 A7A7 A8A8 A9A9
抗静电母粒,添加量Antistatic masterbatch, dosage 3030 3030 3030 3030
抗静电剂antistatic agent -- -- -- --
表面电阻-正面ΩSurface Resistance - Front Ω 10^1010^10 10^810^8 10^1010^10 10^910^9
表面电阻-反面ΩSurface resistance - reverse side Ω 10^1110^11 10^910^9 10^1010^10 10^1010^10
悬臂梁缺口冲击强度kJ/m 2 Izod notched impact strength kJ/m 2 3434 3838 4343 3939
由实施例1-4可知,羧酸基离聚体优选甲基丙烯酸单元中的40mol%-80mol%的羧基被金属离子中和,不仅正反面电阻值更稳定,而且悬臂梁缺口冲击强度更好。From Examples 1-4, it can be seen that 40mol%-80mol% of the carboxyl groups in the carboxylic acid-based ionomer are preferably neutralized by metal ions, so that not only the front and back resistance values are more stable, but also the notched impact strength of the Izod beam is better. .
由实施例1/5/6/7可知,AS树脂优选AN含量为25-28wt%,正反面电阻值更稳定。It can be seen from Examples 1/5/6/7 that the AS resin preferably has an AN content of 25-28 wt%, and the resistance value of the front and back surfaces is more stable.
由实施例1/8/9可知,抗静电剂优选聚环氧乙烷、聚醚酯酰胺,不仅正反面电阻值更稳定,而且悬臂梁缺口冲击强度更好。It can be known from Example 1/8/9 that the antistatic agent is preferably polyethylene oxide or polyether ester amide, not only the front and back resistance values are more stable, but also the Izod notched impact strength is better.
续表5:Continuation of Table 5:
Figure PCTCN2022081587-appb-000003
Figure PCTCN2022081587-appb-000003
由实施例1/10/11可知,蜡类聚合物优选氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡,虽然使用低分子量共聚酰胺蜡的实施例9悬臂梁缺口冲击强度数值较高,但是氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡对于电阻分散均匀性更好。As can be seen from Example 1/10/11, the waxy polymer is preferably oxidized polyethylene wax, maleic anhydride modified polyethylene wax, although the notched Izod impact strength value of Example 9 using low molecular weight copolyamide wax is higher, but Oxidized polyethylene wax and maleic anhydride modified polyethylene wax have better resistance dispersion uniformity.
由实施例1/12-15可知,在优选的配比范围内正反面电阻值更稳定,悬臂梁缺口冲击强度数值也较高。It can be seen from Examples 1/12-15 that the resistance value of the front and back surfaces is more stable in the preferred proportion range, and the Izod notched impact strength value is also higher.
续表5:Continuation of Table 5:
Figure PCTCN2022081587-appb-000004
Figure PCTCN2022081587-appb-000004
由对比例1可知,不添加羧酸基离聚体的抗静电母粒,正反面电阻值差别大,而且电阻值较低。It can be seen from Comparative Example 1 that the antistatic masterbatch without carboxylic acid-based ionomer has a large difference in resistance value between the front and back sides, and the resistance value is relatively low.
由对比例2可知,蜡类聚合物明显影响抗静电剂的分布。It can be seen from Comparative Example 2 that the wax polymer obviously affects the distribution of the antistatic agent.
由对比例3可知,抗静电母粒中不添加AS树脂,不仅正反面电阻值差别大,而且悬臂梁缺口冲击强度低。It can be seen from Comparative Example 3 that if no AS resin is added to the antistatic masterbatch, not only the difference in resistance between the front and back surfaces is large, but also the notched impact strength of the Izod beam is low.
由对比例4/5可知,羧酸基离聚体添加量过低或过高,也很难实现抗静电剂的特定分布(电阻值也较低)。It can be seen from Comparative Example 4/5 that if the amount of carboxylic acid-based ionomer added is too low or too high, it is also difficult to achieve a specific distribution of antistatic agent (the resistance value is also low).
由对比例6可知,直接添加抗静电剂,不仅正反面电阻值不稳定,而且破坏了PC/ABS合金的力学性能。It can be known from Comparative Example 6 that directly adding an antistatic agent not only makes the resistance value of the front and back sides unstable, but also destroys the mechanical properties of the PC/ABS alloy.

Claims (10)

  1. 一种抗静电母粒,其特征在于,按重量份计,包括以下组分:An antistatic masterbatch is characterized in that, by weight, it comprises the following components:
    Figure PCTCN2022081587-appb-100001
    Figure PCTCN2022081587-appb-100001
  2. 根据权利要求1所述的抗静电母粒,其特征在于,按重量份计,包括以下组分:Antistatic masterbatch according to claim 1, is characterized in that, by weight, comprises the following components:
    Figure PCTCN2022081587-appb-100002
    Figure PCTCN2022081587-appb-100002
  3. 根据权利要求1所述的抗静电母粒,其特征在于,所述的羧酸基离聚体为乙烯/甲基丙烯酸类共聚物,其中甲基丙烯酸单元中的25mol%-90mol%的羧基被金属离子中和;优选的,甲基丙烯酸单元中的40mol%-80mol%的羧基被金属离子中和。The antistatic masterbatch according to claim 1, wherein the carboxylic acid-based ionomer is an ethylene/methacrylic acid copolymer, wherein 25mol%-90mol% of the carboxyl groups in the methacrylic acid unit are Metal ion neutralization; preferably, 40mol%-80mol% of carboxyl groups in the methacrylic acid unit are neutralized by metal ions.
  4. 根据权利要求3所述的抗静电母粒,其特征在于,所述的金属离子选自钠离子、锌离子、镁离子、钾离子中的至少一种,所述的羧酸基离聚体的熔融指数在0.5-6g/10min之间,测试条件为190℃、2.16kg。The antistatic masterbatch according to claim 3, wherein the metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion, and potassium ion, and the carboxylic acid-based ionomer The melt index is between 0.5-6g/10min, and the test conditions are 190°C and 2.16kg.
  5. 根据权利要求1所述的抗静电母粒,其特征在于,所述的AS树脂中AN含量为18-36wt%;优选的,AS树脂中AN含量为25-28wt%。The antistatic masterbatch according to claim 1, characterized in that the AN content in the AS resin is 18-36wt%; preferably, the AN content in the AS resin is 25-28wt%.
  6. 根据权利要求1所述的抗静电母粒,其特征在于,所述的抗静电剂选自乙氧基化烷基胺、乙氧基月桂酰胺、甘油酸酯、高级醇硫酸酯盐、聚环氧乙烷、聚醚酯酰胺、聚醚酯酰亚胺中的至少一种;优选的,所述的抗静电剂选自聚环氧乙烷、聚醚酯酰胺中的至少一种。The antistatic masterbatch according to claim 1, wherein the antistatic agent is selected from the group consisting of ethoxylated alkylamines, ethoxylated lauryl amide, glyceric acid esters, higher alcohol sulfate ester salts, polycyclic At least one of ethylene oxide, polyether ester amide, and polyether ester imide; preferably, the antistatic agent is selected from at least one of polyethylene oxide and polyether ester amide.
  7. 根据权利要求1所述的抗静电母粒,其特征在于,所述的蜡类聚合物选自聚乙烯蜡、氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡、低分子量共聚酰胺蜡中的一种或者几种;优选的,所述的蜡类聚合物选自氧化聚乙烯蜡、马来酸酐改性聚乙烯蜡中的至少一种。antistatic masterbatch according to claim 1, is characterized in that, described wax polymer is selected from polyethylene wax, oxidized polyethylene wax, maleic anhydride modified polyethylene wax, low molecular weight copolyamide wax One or more; preferably, the wax polymer is selected from at least one of oxidized polyethylene wax and maleic anhydride modified polyethylene wax.
  8. 根据权利要求1所述的抗静电母粒,其特征在于,按重量份计,还包括0-2份助剂;所述的助剂选自抗氧剂、润滑剂中的至少一种。The antistatic masterbatch according to claim 1, characterized in that, by weight, it also includes 0-2 parts of auxiliary agents; said auxiliary agents are selected from at least one of antioxidants and lubricants.
  9. 权利要求1-8任一项所述的抗静电母粒的制备方法,其特征在于,包括以下步骤:按照配比,将羧酸基离聚体、AS树脂、抗静电剂、蜡类聚合物混和均匀后通过双螺杆挤出机挤出造粒,螺杆温度为200-270℃,转速范围是180-500r/min。The preparation method of the antistatic masterbatch described in any one of claims 1-8, is characterized in that, comprises the following steps: according to proportioning, with carboxylic acid group ionomer, AS resin, antistatic agent, wax polymer After mixing evenly, extrude and granulate through a twin-screw extruder, the screw temperature is 200-270°C, and the speed range is 180-500r/min.
  10. 权利要求1-8任一项所述的抗静电母粒的应用,其特征在于,用于制备抗静电PC/ABS 合金,按重量份计,包括以下组分:The application of the antistatic master batch described in any one of claims 1-8 is characterized in that, for preparing antistatic PC/ABS alloy, by weight, comprising the following components:
    PC树脂      25-75份;PC resin 25-75 parts;
    ABS树脂     25-75份;ABS resin 25-75 parts;
    抗静电母粒  10-45份。Antistatic masterbatch 10-45 parts.
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