WO2022121441A1 - Toughened and wear-resistant polyamide composition, preparation method therefor and use thereof - Google Patents

Toughened and wear-resistant polyamide composition, preparation method therefor and use thereof Download PDF

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WO2022121441A1
WO2022121441A1 PCT/CN2021/119844 CN2021119844W WO2022121441A1 WO 2022121441 A1 WO2022121441 A1 WO 2022121441A1 CN 2021119844 W CN2021119844 W CN 2021119844W WO 2022121441 A1 WO2022121441 A1 WO 2022121441A1
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toughening agent
ethylene
polyamide composition
methacrylic acid
parts
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PCT/CN2021/119844
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French (fr)
Chinese (zh)
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许鸿基
冯德才
黄险波
丁超
郑一泉
王丰
张永
叶坤豪
戴剑
叶南飚
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金发科技股份有限公司
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • 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
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to the technical field of engineering plastics, and more particularly, to a toughened and wear-resistant polyamide composition and a preparation method and application thereof.
  • Polyamide resin has high rigidity, good toughness and good heat distortion temperature, and its forming processability and chemical resistance are relatively good, so it is used as an internal stress member or external structural member in rail transit, consumer appliances, Power tools and other fields have been widely used.
  • the wear resistance enhancement of polyamide is usually achieved by adding wear resistance agents such as molybdenum disulfide and polytetrafluoroethylene. Decrease in material toughness.
  • Cisoka patent application CN111040439A discloses a polyamide material with excellent wear resistance. Through the combination of polyvinyl alcohol, glass fiber, octadecyl isocyanate and other components and polyamide, a toughness-enhancing and wear-resistant material is prepared. Polyamide material. However, the simply supported beam notch impact strength of the toughness-enhancing polyamide material is only 10-12KJ/m 2 , which still cannot meet the current demand for high toughness.
  • the present invention provides a toughened and wear-resistant polyamide composition with excellent wear resistance and toughness in order to overcome the above-mentioned defects of the prior art that high toughness and wear resistance cannot be combined.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polyamide composition.
  • Another object of the present invention is to provide the application of the above-mentioned polyamide composition.
  • the technical scheme adopted in the present invention is:
  • a toughened and wear-resistant polyamide composition comprising the following components by weight:
  • the first toughening agent is maleic anhydride grafted toughening agent
  • the second toughening agent is glycidyl methacrylate as a monomer copolymerized toughening agent and/or glycidyl methacrylate grafted.
  • the weight ratio of the first toughening agent to the second toughening agent is (1-10):1.
  • the aliphatic polyamide is a polyamide formed by the polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine and/or formed by the polycondensation of at least one amino acid or at least one lactam and itself of polyamide.
  • the first toughening agents all contain maleic anhydride functional groups
  • the second toughening agents all contain epoxy functional groups.
  • the toughening agent can react in the polyamide system to form a micro-crosslinked toughening phase, and at the same time form an excellent bonding interface with the polyamide matrix.
  • the maleic anhydride functional group can react with the terminal amino group in the polyamide to form an amide bond
  • the epoxy functional group in the second toughening agent can react with the terminal carboxyl group in the polyamide to form an ester bond
  • the formation of amide bonds and ester bonds is beneficial to improve the interface bonding force between the toughening agent and the polyamide resin, thereby improving the toughness of the material
  • the reaction between the maleic anhydride functional group and the epoxy functional group can also form an ester bond, thus
  • the formation of micro-crosslinks in the toughening phase of the polyamide composition can improve the toughness and wear resistance of the material.
  • the weight ratio of the first toughening agent to the second toughening agent exceeds the range of (1-10):1
  • the micro-crosslinking reaction between the maleic anhydride functional group and the epoxy functional group cannot effectively improve the toughness and resistance of the polyamide material. Grinding performance effect.
  • the weight ratio of the first toughening agent to the second toughening agent is (2-5):1.
  • the inventors have found that when the weight ratio of the first toughening agent to the second toughening agent is (2-5):1, the prepared polyamide composition can obtain better wear resistance and toughness.
  • the first toughening agent is one or more of maleic anhydride grafted polyolefin, ethylene-propylene-non-conjugated diene terpolymer or ethylene-butyl acrylate copolymer
  • the first toughening agent is a maleic anhydride grafted polyolefin elastomer.
  • the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glyceryl methacrylate copolymer or ethylene-butyl acrylate-glycidyl methacrylate copolymer
  • glyceride grafted polyolefin elastomers One or more of glyceride grafted polyolefin elastomers.
  • the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer.
  • the glass fiber is one of E glass fiber, H glass fiber, R glass fiber, S glass fiber, D glass fiber, C glass fiber or quartz glass fiber.
  • the glass fibers are E glass fibers.
  • the ethylene-methacrylic acid ionic polymer refers to a derivative in which part of the acrylic acid functional groups in the ethylene-methacrylic acid copolymer are neutralized by metal cations.
  • the metal cation is zinc ion, sodium ion or potassium ion.
  • the carboxylate ion in the ethylene-methacrylic acid ionic polymer can react with the maleic anhydride functional group to form an ester bond, thereby forming a microphase state with good compatibility;
  • the composition can not only play the role of toughening, but also have a more obvious effect of improving the wear resistance.
  • the polyamide composition has lower abrasion and higher notched impact strength.
  • the ethylene-methacrylic acid ionic polymer is 0.3-2 parts by weight.
  • the ethylene-methacrylic acid ionic polymer is one of the zinc salt of ethylene-methacrylic acid copolymer, the sodium salt of ethylene-methacrylic acid copolymer or the potassium salt of ethylene-methacrylic acid copolymer or several.
  • the ethylene-methacrylic acid ionic polymer is a zinc salt of ethylene-methacrylic acid copolymer.
  • the stabilizer is an antioxidant, a UV absorber or a hindered amine stabilizer.
  • the antioxidant is one or more of hindered phenol antioxidants, alkali metal or alkaline earth metal hypo()phosphites and phosphite ester antioxidants.
  • the ultraviolet absorber is one or more of resorcinol ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers.
  • the hindered amine stabilizer is one or more of a secondary amine stabilizer, a tertiary amine stabilizer, and a NOR stabilizer.
  • the lubricant is higher fatty acid, higher fatty acid metal salt, higher fatty acid ester or higher fatty acid amide.
  • the lubricant is stearic acid, palmitic acid, oleic acid, higher fatty acid sodium salt, higher fatty acid aluminum salt, n-butyl stearate, glyceryl stearate, stearic acid amide, oleic acid One or more of amide and erucamide.
  • the present invention also protects the preparation method of the above-mentioned toughened and wear-resistant polyamide composition, comprising the following steps:
  • the aliphatic polyamide, the first toughening agent, the second toughening agent, the ethylene-methacrylic acid ionomer, the stabilizer, and the lubricant are mixed, added to the main feeding system of the extruder, melted and mixed, and the glass fiber Adding into the side feeding system of the extruder, mixing, extruding and pelletizing to obtain the toughened and wear-resistant polyamide composition.
  • the extruder is a twin-screw extruder
  • the screw length-diameter ratio of the twin-screw extruder is 36-52:1
  • the screw barrel temperature is 180-280°C
  • the screw speed is 200-700 rpm.
  • the present invention also protects the application of the above toughened and wear-resistant polyamide composition in the preparation of internal force-bearing parts or external structural parts of rail transit, consumer appliances, and electric tools.
  • the toughening agent containing maleic anhydride functional group, the toughening agent containing epoxy functional group, glass fiber, aliphatic polyamide and other components are cooperated with each other to prepare a polyamide composition with enhanced toughness and good wear resistance.
  • the prepared polyamide composition has higher toughness, notched Izod impact strength ⁇ 20KJ/m 2 , and excellent wear resistance, using GB/T 5478-2008 Method test wear amount ⁇ 100mg.
  • the raw materials in the embodiment, that is, the comparative example can be obtained through commercially available products, and the details are as follows:
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • Table 1 shows the content of each component in the toughened and wear-resistant polyamide compositions of Examples 1-18.
  • the preparation method is as follows: according to Table 1, the components except the glass fiber are mixed uniformly, then the mixture is added to the main feeding system of the twin-screw extruder, and the glass fiber is added to the side feeding system of the twin-screw extruder,
  • the toughened and wear-resistant polyamide composition was prepared by melt blending and extrusion granulation with a twin-screw extruder; wherein the twin-screw length-diameter ratio was 40:1, the screw barrel temperature was 240° C., and the screw speed was 350 rpm.
  • the preparation method is as follows: according to Table 2, the components except the glass fiber are mixed uniformly, then the mixture is added to the main feeding system of the twin-screw extruder, and the glass fiber is added to the side feeding system of the twin-screw extruder,
  • the toughened and wear-resistant polyamide composition was prepared by melt blending and extrusion granulation with a twin-screw extruder; wherein the twin-screw length-diameter ratio was 40:1, the screw barrel temperature was 240° C., and the screw speed was 350 rpm.
  • the polyamide composition was injection molded into test strips; the test strips were adjusted for 24 hours in a laboratory standard environment of 23°C and 50% RH, and the notched impact strength of the Izod was tested according to the ISO-527-2:2012 standard;
  • the notched Izod impact strength of the polyamide compositions prepared in Examples 1 to 18 is ⁇ 20KJ/m 2
  • the test abrasion amount is ⁇ 100mg using the GB/T 5478-2008 method.
  • the wear amounts of Examples 1 and 2 are relatively lower, only 75 mg and 68 mg respectively; Although the notched impact strength of the polyamide composition reaches 33.7KJ/m 2 , the wear amount is 96 mg. Therefore, considering the toughness and wear resistance of the polyamide composition, the first toughening agent and the second toughening agent The weight ratio of the agent is preferably (2-5):1.
  • the polyamide composition when the polyamide composition further contains ethylene-methacrylic acid ionomer, the polyamide composition can obtain better toughness and lower wear amount , and the ethylene-methacrylic acid ion polymer is preferably 0.3 to 2 parts by weight, and the ethylene-methacrylic acid ion polymer is preferably an ethylene-methacrylic acid zinc ion polymer.
  • the polyamide compositions of Comparative Examples 1 to 3 lack the first toughening agent and/or the second toughening agent, and the wear amount of the polyamide composition is all 100 mg, which is difficult to meet the actual wear resistance requirements;
  • Comparative example 4 contains 2 parts by weight of ethylene-methacrylic acid ionic polymer, but no toughening agent is added, the toughness of the polyamide composition is poor, and the wear amount is too high;
  • the amount of toughening agent is too small, the weight ratio of the first toughening agent to the second toughening agent in Comparative Example 7 is 20:1, and the amount of the second toughening agent in Comparative Example 8 is too large, the obtained polyamide combination None of them have good toughness and wear resistance.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Disclosed are a toughened and wear-resistant polyamide composition, a preparation method therefor and the use thereof. The toughened and wear-resistant polyamide composition comprises the following components: an aliphatic polyamide, glass fibers, a first toughening agent, a second toughening agent, a stabilizer, a lubricant and an ethylene-methacrylic acid ionic polymer, wherein the first toughening agent is a maleic anhydride-grafted toughening agent; the second toughening agent is a toughening agent copolymerized from glycidyl methacrylate as a monomer and/or a toughening agent grafted with glycidyl methacrylate; and the weight ratio of the first toughening agent to the second toughening agent is (1-10) : 1. By means of the present invention, a polyamide composition with enhanced toughness and good wear resistance is prepared by mutual cooperation of the specific toughening agents, the ethylene-methacrylic acid ionic polymer and other components.

Description

一种增韧耐磨聚酰胺组合物及其制备方法和应用A toughened and wear-resistant polyamide composition and its preparation method and application 技术领域technical field
本发明涉及工程塑料技术领域，更具体的，涉及一种增韧耐磨聚酰胺组合物及其制备方法和应用。The present invention relates to the technical field of engineering plastics, and more particularly, to a toughened and wear-resistant polyamide composition and a preparation method and application thereof.
背景技术Background technique
聚酰胺树脂具有较高的刚性、良好的韧性以及较好的热变形温度，并且其成形加工性和耐化学品性比较优良，因此作为内部受力件或外部结构件在轨道交通、消费电器、电动工具等领域得到了广泛地应用。Polyamide resin has high rigidity, good toughness and good heat distortion temperature, and its forming processability and chemical resistance are relatively good, so it is used as an internal stress member or external structural member in rail transit, consumer appliances, Power tools and other fields have been widely used.
随着社会的不断发展进步，以塑代钢的应用场景逐渐增多，且很多产品逐渐往轻薄化的方向发展，部分产品在使用过程中可能长期受到往复摩擦等作用，因此对材料的机械性能、耐磨性能等方面提出了更高的要求。对于聚酰胺的耐磨性能增强，通常是通过添加如二硫化钼、聚四氟乙烯等耐磨剂来实现，但耐磨剂的添加在提升聚酰胺耐磨性能的同时，也会造成聚酰胺材料韧性的下降。With the continuous development and progress of society, the application scenarios of replacing steel with plastic have gradually increased, and many products have gradually developed in the direction of light and thin. Wear resistance and other aspects put forward higher requirements. The wear resistance enhancement of polyamide is usually achieved by adding wear resistance agents such as molybdenum disulfide and polytetrafluoroethylene. Decrease in material toughness.
中国专利申请CN111040439A公开了一种耐磨性能优异的聚酰胺材料，通过聚乙烯醇、玻璃纤维、十八烷基异氰酸酯等组分与聚酰胺的配合，制备得到了韧性增强且具有耐磨性能的聚酰胺材料。但该增强韧性的聚酰胺材料的简支梁缺口冲击强度仅为10～12KJ/m 2，仍无法满足目前的高韧性需求。 Chinese patent application CN111040439A discloses a polyamide material with excellent wear resistance. Through the combination of polyvinyl alcohol, glass fiber, octadecyl isocyanate and other components and polyamide, a toughness-enhancing and wear-resistant material is prepared. Polyamide material. However, the simply supported beam notch impact strength of the toughness-enhancing polyamide material is only 10-12KJ/m 2 , which still cannot meet the current demand for high toughness.
因此，需要开发出一种兼具耐磨性能和高韧性的聚酰胺组合物。Therefore, there is a need to develop a polyamide composition with both wear resistance and high toughness.
发明内容SUMMARY OF THE INVENTION
本发明为克服上述现有技术所述的高韧性和耐磨无法兼具的缺陷，提供一种增韧耐磨的聚酰胺组合物，该聚酰胺组合物具有优异的耐磨性能和韧性。The present invention provides a toughened and wear-resistant polyamide composition with excellent wear resistance and toughness in order to overcome the above-mentioned defects of the prior art that high toughness and wear resistance cannot be combined.
本发明的另一目的在于提供上述聚酰胺组合物的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned polyamide composition.
本发明的另一目的在于提供上述聚酰胺组合物的应用。Another object of the present invention is to provide the application of the above-mentioned polyamide composition.
为解决上述技术问题，本发明采用的技术方案是：In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is:
一种增韧耐磨的聚酰胺组合物，包括如下重量份的组分：A toughened and wear-resistant polyamide composition, comprising the following components by weight:
脂肪族聚酰胺30～75份，30-75 parts of aliphatic polyamide,
玻璃纤维20～40份，20 to 40 parts of glass fiber,
第一增韧剂2～15份，2 to 15 parts of the first toughening agent,
第二增韧剂0.2～5份，0.2 to 5 parts of the second toughening agent,
稳定剂0.05～2份，Stabilizer 0.05 to 2 parts,
润滑剂0.05～2份，Lubricant 0.05 to 2 parts,
乙烯-甲基丙烯酸离子聚合物0～5份；0 to 5 parts of ethylene-methacrylic acid ionic polymer;
所述第一增韧剂为马来酸酐接枝的增韧剂，第二增韧剂为甲基丙烯酸缩水甘油酯作为单体共聚的增韧剂和/或甲基丙烯酸缩水甘油酯接枝的聚烯烃增韧剂；The first toughening agent is maleic anhydride grafted toughening agent, and the second toughening agent is glycidyl methacrylate as a monomer copolymerized toughening agent and/or glycidyl methacrylate grafted. Polyolefin toughening agent;
第一增韧剂与第二增韧剂的重量比为(1～10)∶1。The weight ratio of the first toughening agent to the second toughening agent is (1-10):1.
所述脂肪族聚酰胺为由至少一种脂肪族二元羧酸与至少一种脂肪族二胺缩聚而成的聚酰胺和/或由至少一种氨基酸或至少一种内酰胺与其本身缩聚而成的聚酰胺。The aliphatic polyamide is a polyamide formed by the polycondensation of at least one aliphatic dicarboxylic acid and at least one aliphatic diamine and/or formed by the polycondensation of at least one amino acid or at least one lactam and itself of polyamide.
本发明的技术方案中，第一增韧剂均含有马来酸酐官能团，第二增韧剂均含有环氧官能团，发明人通过研究发现，含有马来酸酐官能团的增韧剂与含有环氧官能团的增韧剂，在聚酰胺体系中能够反应形成微交联的增韧相，同时和聚酰胺基体形成优异的结合界面。In the technical solution of the present invention, the first toughening agents all contain maleic anhydride functional groups, and the second toughening agents all contain epoxy functional groups. The toughening agent can react in the polyamide system to form a micro-crosslinked toughening phase, and at the same time form an excellent bonding interface with the polyamide matrix.
在共混挤出的过程中，马来酸酐官能团可以和聚酰胺中的端氨基发生反应形成酰胺键，第二增韧剂中的环氧官能团可以和聚酰胺中的端羧基发生反应形成酯键，酰胺键和酯键的形成有利于提升增韧剂和聚酰胺树脂的界面结合力，从而提升材料韧性；此外，马来酸酐官能团和环氧官能团之间也能形成反应形成酯键，由此在聚酰胺组合物的增韧相内部形成微交联的作用，可以起到提升材料韧性和耐磨性能的作用。In the process of blending and extrusion, the maleic anhydride functional group can react with the terminal amino group in the polyamide to form an amide bond, and the epoxy functional group in the second toughening agent can react with the terminal carboxyl group in the polyamide to form an ester bond , the formation of amide bonds and ester bonds is beneficial to improve the interface bonding force between the toughening agent and the polyamide resin, thereby improving the toughness of the material; in addition, the reaction between the maleic anhydride functional group and the epoxy functional group can also form an ester bond, thus The formation of micro-crosslinks in the toughening phase of the polyamide composition can improve the toughness and wear resistance of the material.
当第一增韧剂与第二增韧剂的重量比超出(1～10)∶1的范围时，马来酸酐官能团与环氧官能团的微交联反应不能有效提升聚酰胺材料的韧性和耐磨性能效果。When the weight ratio of the first toughening agent to the second toughening agent exceeds the range of (1-10):1, the micro-crosslinking reaction between the maleic anhydride functional group and the epoxy functional group cannot effectively improve the toughness and resistance of the polyamide material. Grinding performance effect.
优选地，所述第一增韧剂与第二增韧剂的重量比为(2～5)∶1。Preferably, the weight ratio of the first toughening agent to the second toughening agent is (2-5):1.
发明人研究发现，当第一增韧剂与第二增韧剂的重量比为(2～5)∶1时，制得的聚酰胺组合物能够获得更优的耐磨性能和韧性。The inventors have found that when the weight ratio of the first toughening agent to the second toughening agent is (2-5):1, the prepared polyamide composition can obtain better wear resistance and toughness.
优选地，所述第一增韧剂为马来酸酐接枝的聚烯烃、乙烯-丙烯-非共轭二烯烃三元共聚物或乙烯-丙烯酸丁酯共聚物中的一种或几种Preferably, the first toughening agent is one or more of maleic anhydride grafted polyolefin, ethylene-propylene-non-conjugated diene terpolymer or ethylene-butyl acrylate copolymer
更优选地，所述第一增韧剂为马来酸酐接枝聚烯烃弹性体。More preferably, the first toughening agent is a maleic anhydride grafted polyolefin elastomer.
优选地，所述第二增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物、 乙烯-丙烯酸甲酯-甲基丙烯酸甘油酯共聚物或乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯接枝聚烯烃弹性体中的一种或几种。Preferably, the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glyceryl methacrylate copolymer or ethylene-butyl acrylate-glycidyl methacrylate copolymer One or more of glyceride grafted polyolefin elastomers.
更优选地，所述第二增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物。More preferably, the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer.
优选地，所述玻璃纤维为E玻璃纤维、H玻璃纤维、R玻璃纤维、S玻璃纤维、D玻璃纤维、C玻璃纤维或石英玻璃纤维中的一种。Preferably, the glass fiber is one of E glass fiber, H glass fiber, R glass fiber, S glass fiber, D glass fiber, C glass fiber or quartz glass fiber.
更优选地，所述玻璃纤维为E玻璃纤维。More preferably, the glass fibers are E glass fibers.
所述乙烯-甲基丙烯酸离子聚合物是指乙烯-甲基丙烯酸共聚物中部分丙烯酸官能团被金属阳离子中和后的衍生物。可选的，所述金属阳离子为锌离子、钠离子或钾离子。The ethylene-methacrylic acid ionic polymer refers to a derivative in which part of the acrylic acid functional groups in the ethylene-methacrylic acid copolymer are neutralized by metal cations. Optionally, the metal cation is zinc ion, sodium ion or potassium ion.
所述乙烯-甲基丙烯酸离子聚合物中的羧酸根离子，可以和马来酸酐官能团反应形成酯键，进而形成具有良好相容性的微相态；乙烯-甲基丙烯酸离子聚合物在聚酰胺组合物中既可以起到增韧的作用，同时对耐磨性能有更明显的提升作用。The carboxylate ion in the ethylene-methacrylic acid ionic polymer can react with the maleic anhydride functional group to form an ester bond, thereby forming a microphase state with good compatibility; The composition can not only play the role of toughening, but also have a more obvious effect of improving the wear resistance.
在本发明技术方案中第一增韧剂和第二增韧剂的共同作用下，进一步复合乙烯-甲基丙烯酸离子聚合物，可以获得更好的增韧、耐磨协效作用，制得的聚酰胺组合物的磨耗量更低、缺口冲击强度更高。Under the joint action of the first toughening agent and the second toughening agent in the technical solution of the present invention, further compounding the ethylene-methacrylic acid ionic polymer can obtain better synergistic effects of toughening and wear resistance. The polyamide composition has lower abrasion and higher notched impact strength.
优选地，所述乙烯-甲基丙烯酸离子聚合物为0.3～2重量份。Preferably, the ethylene-methacrylic acid ionic polymer is 0.3-2 parts by weight.
优选地，所述乙烯-甲基丙烯酸离子聚合物为乙烯-甲基丙烯酸共聚物的锌盐、乙烯-甲基丙烯酸共聚物的钠盐或乙烯-甲基丙烯酸共聚物的钾盐中的一种或几种。Preferably, the ethylene-methacrylic acid ionic polymer is one of the zinc salt of ethylene-methacrylic acid copolymer, the sodium salt of ethylene-methacrylic acid copolymer or the potassium salt of ethylene-methacrylic acid copolymer or several.
更优选的，所述乙烯-甲基丙烯酸离子聚合物为乙烯-甲基丙烯酸共聚物的锌盐。More preferably, the ethylene-methacrylic acid ionic polymer is a zinc salt of ethylene-methacrylic acid copolymer.
优选地，所述稳定剂为抗氧剂、紫外吸收剂或受阻胺类稳定剂。Preferably, the stabilizer is an antioxidant, a UV absorber or a hindered amine stabilizer.
优选地，所述抗氧剂为受阻酚抗氧剂、碱金属或碱土金属次(亚)磷酸盐和亚磷酸酯类抗氧剂中的一种或几种。Preferably, the antioxidant is one or more of hindered phenol antioxidants, alkali metal or alkaline earth metal hypo()phosphites and phosphite ester antioxidants.
优选地，所述紫外吸收剂为间苯二酚类紫外吸收剂、水杨酸酯紫外吸收剂、苯并三唑紫外吸收剂或二苯甲酮紫外吸收剂中一种或几种。Preferably, the ultraviolet absorber is one or more of resorcinol ultraviolet absorbers, salicylate ultraviolet absorbers, benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers.
优选地，所述受阻胺类稳定剂为仲胺类稳定剂、叔胺类稳定剂、NOR类稳定剂中的一种或几种。Preferably, the hindered amine stabilizer is one or more of a secondary amine stabilizer, a tertiary amine stabilizer, and a NOR stabilizer.
优选地，所述润滑剂为高级脂肪酸、高级脂肪酸金属盐、高级脂肪酸酯或高级脂肪酸酰胺。Preferably, the lubricant is higher fatty acid, higher fatty acid metal salt, higher fatty acid ester or higher fatty acid amide.
可选的，所述润滑剂为硬脂酸、软脂酸、油酸、高级脂肪酸钠盐、高级脂肪酸铝盐、硬脂酸正丁酯、硬脂酸甘油酯、硬脂酸酰胺、油酸酰胺、芥酸酰胺中的一种或几种。Optionally, the lubricant is stearic acid, palmitic acid, oleic acid, higher fatty acid sodium salt, higher fatty acid aluminum salt, n-butyl stearate, glyceryl stearate, stearic acid amide, oleic acid One or more of amide and erucamide.
本发明还保护上述增韧耐磨的聚酰胺组合物的制备方法，包括如下步骤：The present invention also protects the preparation method of the above-mentioned toughened and wear-resistant polyamide composition, comprising the following steps:
将脂肪族聚酰胺、第一增韧剂、第二增韧剂、乙烯-甲基丙烯酸离子聚合物、稳定剂、润滑剂混合，加入挤出机的主喂料系统，熔融混合，将玻璃纤维加入挤出机的侧喂料系统，混合挤出造粒，得到所述增韧耐磨的聚酰胺组合物。The aliphatic polyamide, the first toughening agent, the second toughening agent, the ethylene-methacrylic acid ionomer, the stabilizer, and the lubricant are mixed, added to the main feeding system of the extruder, melted and mixed, and the glass fiber Adding into the side feeding system of the extruder, mixing, extruding and pelletizing to obtain the toughened and wear-resistant polyamide composition.
优选地，所述挤出机为双螺杆挤出机，双螺杆挤出机的螺杆长径比为36～52:1，螺筒温度为180～280℃，螺杆转速为200～700rpm。Preferably, the extruder is a twin-screw extruder, the screw length-diameter ratio of the twin-screw extruder is 36-52:1, the screw barrel temperature is 180-280°C, and the screw speed is 200-700 rpm.
本发明还保护上述增韧耐磨的聚酰胺组合物在制备轨道交通、消费电器、电动工具的内部受力件或外部结构件中的应用。The present invention also protects the application of the above toughened and wear-resistant polyamide composition in the preparation of internal force-bearing parts or external structural parts of rail transit, consumer appliances, and electric tools.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明将含有马来酸酐官能团的增韧剂、含有环氧官能团的增韧剂与玻璃纤维、脂肪族聚酰胺及其他组分互相配合制备得到了韧性增强同时耐磨性能良好的聚酰胺组合物。在进一步复合乙烯-甲基丙烯酸离子聚合物的情况下，制得的聚酰胺组合物韧性更高，悬梁臂缺口冲击强度≥20KJ/m 2，且耐磨性能优异，使用GB/T 5478-2008方法测试磨耗量≤100mg。 In the present invention, the toughening agent containing maleic anhydride functional group, the toughening agent containing epoxy functional group, glass fiber, aliphatic polyamide and other components are cooperated with each other to prepare a polyamide composition with enhanced toughness and good wear resistance. . In the case of further compounding the ethylene-methacrylic acid ionomer, the prepared polyamide composition has higher toughness, notched Izod impact strength ≥20KJ/m 2 , and excellent wear resistance, using GB/T 5478-2008 Method test wear amount≤100mg.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步的说明。The present invention will be further described below in conjunction with specific embodiments.
实施例即对比例中的原料均可通过市售得到，具体如下：The raw materials in the embodiment, that is, the comparative example, can be obtained through commercially available products, and the details are as follows:
Figure PCTCN2021119844-appb-000001
Figure PCTCN2021119844-appb-000001
Figure PCTCN2021119844-appb-000002
Figure PCTCN2021119844-appb-000002
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
实施例1～18Examples 1 to 18
实施例1～18的增韧耐磨的聚酰胺组合物中各组分的含量如表1所示。Table 1 shows the content of each component in the toughened and wear-resistant polyamide compositions of Examples 1-18.
其制备方法为：根据表1将除玻璃纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统，将玻璃纤维加入双螺杆挤出机的侧喂料系统，通过双螺杆挤出机熔融共混、挤出造粒制备得到增韧耐磨的聚酰胺组合物；其中，双螺杆长径比为40:1，螺筒温度为240℃，螺杆转速为350rpm。The preparation method is as follows: according to Table 1, the components except the glass fiber are mixed uniformly, then the mixture is added to the main feeding system of the twin-screw extruder, and the glass fiber is added to the side feeding system of the twin-screw extruder, The toughened and wear-resistant polyamide composition was prepared by melt blending and extrusion granulation with a twin-screw extruder; wherein the twin-screw length-diameter ratio was 40:1, the screw barrel temperature was 240° C., and the screw speed was 350 rpm.
表1实施例1～18的增韧耐磨的聚酰胺组合物的组分含量(重量份)Table 1 Component content (parts by weight) of the toughened and wear-resistant polyamide compositions of Examples 1 to 18
Figure PCTCN2021119844-appb-000003
Figure PCTCN2021119844-appb-000003
表1续实施例1～18的增韧耐磨的聚酰胺组合物的组分含量(重量份)Table 1 Continuation of Examples 1-18 Toughened and Wear-Resistant Polyamide Compositions Component Content (Parts by Weight)
Figure PCTCN2021119844-appb-000004
Figure PCTCN2021119844-appb-000004
对比例1～8Comparative Examples 1 to 8
对比例1～8的聚酰胺组合物中各组分的含量如表2所示。The content of each component in the polyamide compositions of Comparative Examples 1 to 8 is shown in Table 2.
其制备方法为：根据表2将除玻璃纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统，将玻璃纤维加入双螺杆挤出机的侧喂料系统，通过双螺杆挤出机熔融共混、挤出造粒制备得到增韧耐磨的聚酰胺组合物；其中，双螺杆长径比为40:1，螺筒温度为240℃，螺杆转速为350rpm。The preparation method is as follows: according to Table 2, the components except the glass fiber are mixed uniformly, then the mixture is added to the main feeding system of the twin-screw extruder, and the glass fiber is added to the side feeding system of the twin-screw extruder, The toughened and wear-resistant polyamide composition was prepared by melt blending and extrusion granulation with a twin-screw extruder; wherein the twin-screw length-diameter ratio was 40:1, the screw barrel temperature was 240° C., and the screw speed was 350 rpm.
表2对比例1～8的增韧耐磨的聚酰胺组合物的组分含量(重量份)Table 2 Component content (parts by weight) of the toughened and wear-resistant polyamide compositions of Comparative Examples 1 to 8
Figure PCTCN2021119844-appb-000005
Figure PCTCN2021119844-appb-000005
Figure PCTCN2021119844-appb-000006
Figure PCTCN2021119844-appb-000006
性能测试Performance Testing
(1)悬臂梁缺口冲击强度的测试方法：(1) Test method for notched impact strength of cantilever beam:
将聚酰胺组合物注塑成测试样条；测试样条在23℃、50％RH实验室标准环境中调节24h后按照ISO-527-2:2012标准测试悬臂梁缺口冲击强度；The polyamide composition was injection molded into test strips; the test strips were adjusted for 24 hours in a laboratory standard environment of 23°C and 50% RH, and the notched impact strength of the Izod was tested according to the ISO-527-2:2012 standard;
(2)耐磨性能的测试方法：按照GB/T 5478-2008标准，采用砂轮类型为H18，负载为1kg，记录最终的磨耗量作为耐磨性能评价标准。(2) Test method for wear resistance: According to the GB/T 5478-2008 standard, the grinding wheel type is H18, the load is 1kg, and the final wear amount is recorded as the wear resistance evaluation standard.
测试结果Test Results
各实施例的聚酰胺组合物的性能测试结果见表3，各对比例的聚酰胺组合物的性能测试结果见表4。The performance test results of the polyamide compositions of each embodiment are shown in Table 3, and the performance test results of the polyamide compositions of each comparative example are shown in Table 4.
表3实施例1～18的性能测试结果Table 3 Performance test results of Examples 1 to 18
Figure PCTCN2021119844-appb-000007
Figure PCTCN2021119844-appb-000007
根据表3的测试结果，实施例1～18制得的聚酰胺组合物悬梁臂缺口冲击强度≥20KJ/m 2，使用GB/T 5478-2008方法测试磨耗量≤100mg。 According to the test results in Table 3, the notched Izod impact strength of the polyamide compositions prepared in Examples 1 to 18 is ≥20KJ/m 2 , and the test abrasion amount is ≤100mg using the GB/T 5478-2008 method.
由实施例1～6可以看出，在悬梁臂缺口冲击强度均满足≥20KJ/m 2的情况下，实施例1、2的磨耗量相对更低，分别仅为75mg、68mg；实施例6的聚酰胺组合物虽然臂梁缺口冲击强度达到33.7KJ/m 2，但磨耗量较高为96mg；因此，综合考虑聚酰胺组合物的韧性和耐磨性能，第一增韧剂与第二增韧剂的重量比优选为(2～5)∶1。由实施例7～9，当第一增韧剂为马来酸酐接枝聚烯烃弹性体、第二增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯时，聚酰胺组合物的韧性和耐磨性能更优。 It can be seen from Examples 1 to 6 that under the condition that the notched impact strength of the Izod satisfies ≥20KJ/m 2 , the wear amounts of Examples 1 and 2 are relatively lower, only 75 mg and 68 mg respectively; Although the notched impact strength of the polyamide composition reaches 33.7KJ/m 2 , the wear amount is 96 mg. Therefore, considering the toughness and wear resistance of the polyamide composition, the first toughening agent and the second toughening agent The weight ratio of the agent is preferably (2-5):1. From Examples 7 to 9, when the first toughening agent is maleic anhydride grafted polyolefin elastomer and the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate, the toughness of the polyamide composition is and better wear resistance.
由实施例10～13与实施例1的测试结果对比，当所述聚酰胺组合物还含有乙烯-甲基丙烯酸离子聚合物时，聚酰胺组合物能够获得更好的韧性和更低的磨耗量，且乙烯-甲基丙烯酸离子聚合物优选0.3～2重量份，乙烯-甲基丙烯酸离子聚合物优选为乙烯-甲基丙烯酸锌离子聚合物。Comparing the test results of Examples 10-13 with those of Example 1, when the polyamide composition further contains ethylene-methacrylic acid ionomer, the polyamide composition can obtain better toughness and lower wear amount , and the ethylene-methacrylic acid ion polymer is preferably 0.3 to 2 parts by weight, and the ethylene-methacrylic acid ion polymer is preferably an ethylene-methacrylic acid zinc ion polymer.
表4对比例1～8的性能测试结果Table 4 Performance test results of comparative examples 1 to 8
Figure PCTCN2021119844-appb-000008
Figure PCTCN2021119844-appb-000008
根据表4的测试结果，对比例1～3的聚酰胺组合物中缺少第一增韧剂和/或第二增韧剂，聚酰胺组合物的磨耗量均100mg，难以满足实际耐磨需求；对比例4中含有2重量份的乙烯-甲基丙烯酸离子聚合物，但未添加任何增韧剂，聚酰胺组合物的韧性较差，磨耗量也过高；对比例5～6中第一增韧剂的量过少、对比例7中第一增韧剂与第二增韧剂的重量比为20∶1、对比例8中第二增韧剂的量过多，制得的聚酰胺组合物均无法兼具良好的韧性和耐磨性能。According to the test results in Table 4, the polyamide compositions of Comparative Examples 1 to 3 lack the first toughening agent and/or the second toughening agent, and the wear amount of the polyamide composition is all 100 mg, which is difficult to meet the actual wear resistance requirements; Comparative example 4 contains 2 parts by weight of ethylene-methacrylic acid ionic polymer, but no toughening agent is added, the toughness of the polyamide composition is poor, and the wear amount is too high; The amount of toughening agent is too small, the weight ratio of the first toughening agent to the second toughening agent in Comparative Example 7 is 20:1, and the amount of the second toughening agent in Comparative Example 8 is too large, the obtained polyamide combination None of them have good toughness and wear resistance.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

  1. 一种增韧耐磨聚酰胺组合物，其特征在于，包括如下重量份的组分：A toughened and wear-resistant polyamide composition, characterized in that it comprises the following components by weight:
    脂肪族聚酰胺30～75份，玻璃纤维20～40份，第一增韧剂2～15份，第二增韧剂0.2～5份，稳定剂0.05～2份，润滑剂0.05～2份，乙烯-甲基丙烯酸离子聚合物0～5份；Aliphatic polyamide 30-75 parts, glass fiber 20-40 parts, first toughening agent 2-15 parts, second toughening agent 0.2-5 parts, stabilizer 0.05-2 parts, lubricant 0.05-2 parts, 0 to 5 parts of ethylene-methacrylic acid ionic polymer;
    其中第一增韧剂为马来酸酐接枝的增韧剂，第二增韧剂为甲基丙烯酸缩水甘油酯作为单体共聚的增韧剂和/或甲基丙烯酸缩水甘油酯接枝的增韧剂；The first toughening agent is maleic anhydride grafted toughening agent, and the second toughening agent is glycidyl methacrylate as a monomer copolymerized toughening agent and/or glycidyl methacrylate grafted toughening agent toughener;
    第一增韧剂与第二增韧剂的重量比为(1～10)∶1。The weight ratio of the first toughening agent to the second toughening agent is (1-10):1.
  2. 根据权利要求1所述聚酰胺组合物，其特征在于，所述第一增韧剂与第二增韧剂的重量比为(2～5)∶1。The polyamide composition according to claim 1, wherein the weight ratio of the first toughening agent to the second toughening agent is (2-5):1.
  3. 根据权利要求1所述聚酰胺组合物，其特征在于，所述第一增韧剂为马来酸酐接枝聚烯烃弹性体、马来酸酐接枝乙烯-丙烯-非共轭二烯烃三元共聚物或马来酸酐接枝乙烯-丙烯酸丁酯共聚物中的一种或几种。The polyamide composition according to claim 1, wherein the first toughening agent is maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene-propylene-non-conjugated diene terpolymer One or more of the grafted ethylene-butyl acrylate copolymer or maleic anhydride.
  4. 根据权利要求3所述聚酰胺组合物，其特征在于，所述第一增韧剂为马来酸酐接枝聚烯烃弹性体。The polyamide composition according to claim 3, wherein the first toughening agent is a maleic anhydride grafted polyolefin elastomer.
  5. 根据权利要求1所述聚酰胺组合物，其特征在于，所述第二增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物、乙烯-丙烯酸甲酯-甲基丙烯酸甘油酯共聚物或乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯接枝聚烯烃弹性体中的一种或几种。The polyamide composition according to claim 1, wherein the second toughening agent is ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glyceryl methacrylate copolymer one or more of ethylene-butyl acrylate-glycidyl methacrylate grafted polyolefin elastomers.
  6. 根据权利要求5所述聚酰胺组合物，其特征在于，所述第二增韧剂为乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物。The polyamide composition according to claim 5, wherein the second toughening agent is an ethylene-butyl acrylate-glycidyl methacrylate copolymer.
  7. 根据权利要求1所述聚酰胺组合物，其特征在于，所述乙烯-甲基丙烯酸离子聚合物为0.3～2重量份。The polyamide composition according to claim 1, wherein the ethylene-methacrylic acid ionomer is 0.3-2 parts by weight.
  8. 根据权利要求1所述聚酰胺组合物，其特征在于，所述乙烯-甲基丙烯酸离子聚合物为乙烯-甲基丙烯酸共聚物的锌盐、乙烯-甲基丙烯酸共聚物的钠盐或乙烯-甲基丙烯酸共聚物的钾盐中的一种或几种。The polyamide composition according to claim 1, wherein the ethylene-methacrylic acid ionic polymer is a zinc salt of an ethylene-methacrylic acid copolymer, a sodium salt of an ethylene-methacrylic acid copolymer or an ethylene-methacrylic acid copolymer. One or more of the potassium salts of methacrylic acid copolymers.
  9. 权利要求1～8任一项所述聚酰胺组合物的制备方法，其特征在于，包括如下步骤：The preparation method of the polyamide composition according to any one of claims 1 to 8, characterized in that, comprising the steps of:
    将脂肪族聚酰胺、第一增韧剂、第二增韧剂、乙烯-甲基丙烯酸离子聚合物、稳定剂、润滑剂混合，加入挤出机的主喂料系统，熔融混合，将玻璃纤维加入挤 出机的侧喂料系统，混合挤出造粒，得到所述增韧耐磨的聚酰胺组合物。The aliphatic polyamide, the first toughening agent, the second toughening agent, the ethylene-methacrylic acid ionomer, the stabilizer, and the lubricant are mixed, added to the main feeding system of the extruder, melted and mixed, and the glass fiber Adding into the side feeding system of the extruder, mixing, extruding and pelletizing to obtain the toughened and wear-resistant polyamide composition.
  10. 权利要求1～8任一项所述聚酰胺组合物在制备轨道交通、消费电器、电动工具的内部受力件或外部结构件中的应用。Application of the polyamide composition according to any one of claims 1 to 8 in the preparation of internal force-bearing parts or external structural parts of rail transit, consumer electrical appliances, and electric tools.
PCT/CN2021/119844 2020-12-08 2021-09-23 Toughened and wear-resistant polyamide composition, preparation method therefor and use thereof WO2022121441A1 (en)

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