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CN118146598A - Oil-resistant polyvinyl chloride cable - Google Patents

Oil-resistant polyvinyl chloride cable Download PDF

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CN118146598A
CN118146598A CN202410405772.7A CN202410405772A CN118146598A CN 118146598 A CN118146598 A CN 118146598A CN 202410405772 A CN202410405772 A CN 202410405772A CN 118146598 A CN118146598 A CN 118146598A
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polyvinyl chloride
oil
nitrile rubber
chloride cable
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CN118146598B (en
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陈冠瑜
曾广彬
曾秀娟
陈辉
吴连君
吴正俊
吴连飞
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Yangzhou City Hongqi Cable Making Co ltd
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Yangzhou City Hongqi Cable Making Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/14Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

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  • Organic Insulating Materials (AREA)

Abstract

The invention relates to the technical field of cables, in particular to an oil-resistant polyvinyl chloride cable. The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials: polyvinyl chloride, carboxyl butyl rubber or modified nitrile rubber, styrene elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, antioxidant, vulcanizing agent, maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide. According to the invention, the modified nitrile rubber is added into the sheath layer, so that the problems of poor oil resistance, poor wear resistance and poor mechanical properties of the polyvinyl chloride cable are effectively solved, the strength and toughness of the oil-resistant polyvinyl chloride cable are effectively improved, and the oil resistance and wear resistance are also improved.

Description

一种耐油聚氯乙烯电缆Oil-resistant polyvinyl chloride cable

技术领域Technical Field

本发明涉及电缆技术领域,具体涉及一种耐油聚氯乙烯电缆。The invention relates to the technical field of cables, and in particular to an oil-resistant polyvinyl chloride cable.

背景技术Background technique

聚氯乙烯具有较好的绝缘性能、力学性能和加工性能等,被广泛用于电线电缆的绝缘材料和护套材料。但聚氯乙烯的硬度较大,为制备电线电缆用聚氯乙烯软质塑料,通常在聚氯乙烯中加入增塑剂提高其可塑性,保证聚氯乙烯塑料具有一定的柔软性。聚氯乙烯是由聚氯乙烯氯化得到的改性材料,氯含量高于聚氯乙烯树脂,一般65%以上。氯含量的提高,极性增强,赋予了一系列优异性能。与聚氯乙烯比较,强度高、耐热、耐腐蚀、热膨胀系数小、难燃、氧气透过率低,用于高压和特高压电缆敷设套管,能够满足耐热、阻燃、抗压、施工等方面的要求,是性能优良的材料。但是聚氯乙烯难塑化,制成品的冲击强度低,在电力电缆套管中应用,尤其是大口径电力电缆套管中,需要针对其加工性、冲击性能等具体技术要求,对聚氯乙烯材料进行改性。Polyvinyl chloride has good insulation properties, mechanical properties and processing properties, and is widely used as insulation material and sheath material for wires and cables. However, polyvinyl chloride has a large hardness. In order to prepare polyvinyl chloride soft plastic for wires and cables, plasticizers are usually added to polyvinyl chloride to improve its plasticity and ensure that polyvinyl chloride plastic has a certain degree of softness. Polyvinyl chloride is a modified material obtained by chlorination of polyvinyl chloride, and its chlorine content is higher than that of polyvinyl chloride resin, generally more than 65%. The increase in chlorine content enhances polarity and gives it a series of excellent properties. Compared with polyvinyl chloride, it has high strength, heat resistance, corrosion resistance, small thermal expansion coefficient, flame retardancy, and low oxygen permeability. It is used for high-voltage and ultra-high voltage cable laying casings, and can meet the requirements of heat resistance, flame retardancy, pressure resistance, construction, etc. It is a material with excellent performance. However, polyvinyl chloride is difficult to plasticize, and the impact strength of the finished product is low. When used in power cable casings, especially large-diameter power cable casings, it is necessary to modify the polyvinyl chloride material according to specific technical requirements such as its processability and impact performance.

中国发明专利CN116814021B公开了一种高强度耐磨电缆,该电缆由集束线芯和耐磨护套组成,其中,耐磨护套按照重量份计包括:聚氯乙烯树脂100份、高密度聚乙烯15-25份、乙烯-辛烯共聚物8-12份、耐温强化剂10-15份、耐磨填料7-11份、润滑剂3-5份、增韧剂5-8份和抗氧剂0.2-0.3份。尽管该发明有效解决了电缆的耐磨性能,但是该发明中的电缆耐油性能不佳,同时机械强度还有待提高。Chinese invention patent CN116814021B discloses a high-strength wear-resistant cable, which consists of a bundled core and a wear-resistant sheath, wherein the wear-resistant sheath includes, by weight: 100 parts of polyvinyl chloride resin, 15-25 parts of high-density polyethylene, 8-12 parts of ethylene-octene copolymer, 10-15 parts of temperature-resistant enhancer, 7-11 parts of wear-resistant filler, 3-5 parts of lubricant, 5-8 parts of toughening agent and 0.2-0.3 parts of antioxidant. Although the invention effectively solves the wear resistance of the cable, the oil resistance of the cable in the invention is poor, and the mechanical strength needs to be improved.

发明内容Summary of the invention

针对上述现有技术中电缆材料的机械强度和耐油性能存在的不足,本发明提供了一种耐油聚氯乙烯电缆。In view of the deficiencies in mechanical strength and oil resistance of cable materials in the above-mentioned prior art, the present invention provides an oil-resistant polyvinyl chloride cable.

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 technical problems, the technical solution adopted by the present invention is:

一种耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下原料组成:聚氯乙烯、羧基丁基橡胶或改性丁腈橡胶、苯乙烯系弹性体、苯胺甲醛树脂、乙烯基三甲氧基硅烷、抗氧剂、硫化剂、马来酸酐-苯乙烯共聚物、硬脂酸锌、癸二酸二辛酯、液体石蜡、白炭黑和氧化锌。An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials: polyvinyl chloride, carboxybutyl rubber or modified nitrile rubber, styrene elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, antioxidant, vulcanizing agent, maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide.

优选的,所述耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下重量份原料组成:聚氯乙烯60-120份、羧基丁基橡胶或改性丁腈橡胶15-30份、苯乙烯系弹性体10-30份、苯胺甲醛树脂5-12份、乙烯基三甲氧基硅烷5-12份、抗氧剂2-4份、硫化剂1-3份、马来酸酐-苯乙烯共聚物5-12份、硬脂酸锌1-3份、癸二酸二辛酯2-5份、液体石蜡5-10份、白炭黑5-15份和氧化锌10-30份。Preferably, the oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, and the sheath layer is composed of the following raw materials in parts by weight: 60-120 parts of polyvinyl chloride, 15-30 parts of carboxybutyl rubber or modified nitrile rubber, 10-30 parts of styrene elastomer, 5-12 parts of aniline formaldehyde resin, 5-12 parts of vinyl trimethoxy silane, 2-4 parts of antioxidant, 1-3 parts of vulcanizing agent, 5-12 parts of maleic anhydride-styrene copolymer, 1-3 parts of zinc stearate, 2-5 parts of dioctyl sebacate, 5-10 parts of liquid paraffin, 5-15 parts of white carbon black and 10-30 parts of zinc oxide.

所述导体为铜、锌、铁中的任一种。The conductor is any one of copper, zinc and iron.

所述硫化剂为双叔丁基过氧异丙基苯、过氧化二异丙苯、叔丁基苯酚甲醛树脂中的任一种。The vulcanizing agent is any one of di-tert-butyl peroxyisopropylbenzene, diisopropylbenzene peroxide and tert-butylphenol formaldehyde resin.

所述抗氧剂为抗氧剂1010、抗氧剂168、抗氧剂1080、抗氧剂1076中的任一种。The antioxidant is any one of antioxidant 1010, antioxidant 168, antioxidant 1080, and antioxidant 1076.

由于聚氯乙烯难塑化,制成品的冲击强度低、韧性表现较差、耐油性能不佳,在电力电缆套管中应用,尤其是用在耐油电缆套管中,由于其耐油、加工性、冲击性能等不佳,导致使用寿命偏短,并且还易造成电缆在储存和使用中出现开裂等缺陷。Since polyvinyl chloride is difficult to plasticize, the finished product has low impact strength, poor toughness and poor oil resistance. When used in power cable sheaths, especially oil-resistant cable sheaths, it has a short service life due to its poor oil resistance, processability and impact performance. It is also easy to cause defects such as cracking in cables during storage and use.

丁腈橡胶分子结构中具有不饱和双键和氰基,因此具有耐油性交好,耐磨性能好,粘接力强的优点,广泛用于制各种耐油橡胶制品。羧基丁腈橡胶的极性较高,增大了与聚氯乙烯、基体等极性材料的相容性,并使耐油性进一步提升;同时,羧基的引入也提高了材料的拉伸强度,特别是提高了高温下的拉伸强度。本发明旨在其中加入了耐油、耐磨和粘结强的羧基丁腈橡胶,可以提高丁腈橡胶与原料基体的相容性能,可以在一定程度上提高聚氯乙烯电缆材料的耐油性能,虽然羧基丁腈橡胶在耐油性方面表现良好,但在某些方面可能不如聚氯乙烯那样具有良好的可塑性和弹性,这可能会影响电缆在安装和使用过程中的柔韧性和耐久性。The molecular structure of nitrile rubber has unsaturated double bonds and cyano groups, so it has the advantages of good oil resistance, good wear resistance and strong adhesion, and is widely used in the manufacture of various oil-resistant rubber products. The polarity of carboxyl nitrile rubber is relatively high, which increases the compatibility with polar materials such as polyvinyl chloride and matrix, and further improves the oil resistance; at the same time, the introduction of carboxyl groups also improves the tensile strength of the material, especially the tensile strength at high temperatures. The present invention aims to add carboxyl nitrile rubber with oil resistance, wear resistance and strong adhesion, which can improve the compatibility of nitrile rubber with the raw material matrix, and can improve the oil resistance of polyvinyl chloride cable materials to a certain extent. Although carboxyl nitrile rubber performs well in oil resistance, it may not have good plasticity and elasticity like polyvinyl chloride in some aspects, which may affect the flexibility and durability of the cable during installation and use.

所述羧基丁腈橡胶的制备方法如下:将60-120重量份水、1-3重量份烷基酚聚氧乙烯聚氧丙烯醚、10-25重量份丙烯腈、10-25重量份甲基丙烯酸、0.1-0.3重量份乙二胺四乙酸四钠盐、2-5重量份正十二烷基叔硫醇、2-5重量份十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,在200-600rpm、40-50℃下搅拌20-40min,再加入20-40重量份丁二烯和0.5-2重量份偶氮二异丁腈,继续反应40-80min,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到羧基丁腈橡胶。The preparation method of the carboxylated nitrile rubber is as follows: 60-120 parts by weight of water, 1-3 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 10-25 parts by weight of acrylonitrile, 10-25 parts by weight of methacrylic acid, 0.1-0.3 parts by weight of ethylenediaminetetraacetic acid tetrasodium salt, 2-5 parts by weight of n-dodecyl tertiary mercaptan, and 2-5 parts by weight of sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred at 200-600 rpm and 40-50° C. for 20-40 minutes, then 20-40 parts by weight of butadiene and 0.5-2 parts by weight of azobisisobutyronitrile are added, the reaction is continued for 40-80 minutes, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain the carboxylated nitrile rubber.

羧基丁腈橡胶由于无法结晶、橡胶分子间作用力小等特性,会造成其多项性能相对较差,尤其是耐油性能与尺寸稳定性,以其为基础材料制成的电缆材料的工作寿命会大幅度缩短,因此,本发明通过对羧基丁晴橡胶进行了进一步的改性处理,并配合纳米填料的相互作用,大幅度的提高了聚氯乙烯电缆材料的性能,尤其是耐油性能、耐磨、机械性能均具有大幅度的提高,从而显著的提高了电缆的工作寿命。Due to the characteristics of carboxylated nitrile rubber such as inability to crystallize and small intermolecular force of rubber, many of its properties are relatively poor, especially oil resistance and dimensional stability. The working life of cable materials made with it as the basic material will be greatly shortened. Therefore, the present invention further modifies the carboxylated nitrile rubber and cooperates with the interaction of nanofillers to greatly improve the performance of polyvinyl chloride cable materials, especially oil resistance, wear resistance and mechanical properties, thereby significantly improving the working life of the cable.

本发明通过对羧基丁腈橡胶进行了进一步改性处理,过程是以2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸和2-甲氧基-4-乙烯基苯酚反应,得到超分子聚合物作为改性剂,超分子聚合物包括基于多种分子间相互作用以及它们的协同作用或多重作用形成的聚合物,利用超分子聚合物中的氨基和羟基与羧基丁腈橡胶羧基反应,羧基与氨基或羟基缩合形成酰胺键或酯基,得到的改性丁腈橡胶,改性后的羧基丁腈橡胶受力拉伸时,超分子聚合物自身的羟基和氨基之间的氢键以及超分子聚合物与羧基丁腈橡胶之间的氢键优先于共价键断裂耗散能量,氢键的断裂会避免共价键交联的羧基丁腈橡胶因应力集中而过早地被破坏,从而显著提升羧基丁腈橡胶的强度和韧性,同时还能提高耐油性能和耐磨性能。The invention further modifies the carboxylated nitrile rubber, wherein 2-(methacrylate)ethyl 3,5-diaminobenzoic acid and 2-methoxy-4-vinylphenol are reacted to obtain a supramolecular polymer as a modifier, wherein the supramolecular polymer includes a polymer formed based on multiple intermolecular interactions and their synergistic or multiple effects, and an amino group and a hydroxyl group in the supramolecular polymer react with a carboxylated nitrile rubber carboxyl group, and the carboxyl group condenses with the amino group or the hydroxyl group to form an amide bond or an ester group to obtain a modified nitrile rubber. When the modified carboxylated nitrile rubber is stretched under stress, hydrogen bonds between the hydroxyl group and the amino group of the supramolecular polymer itself and hydrogen bonds between the supramolecular polymer and the carboxylated nitrile rubber break and dissipate energy before covalent bonds break, and the breaking of hydrogen bonds prevents the covalently cross-linked carboxylated nitrile rubber from being destroyed prematurely due to stress concentration, thereby significantly improving the strength and toughness of the carboxylated nitrile rubber, and also improving the oil resistance and wear resistance.

优选的,所述改性丁腈橡胶的制备方法如下:Preferably, the preparation method of the modified nitrile rubber is as follows:

S1将2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸、2-甲氧基-4-乙烯基苯酚与N,N-二甲基甲酰胺混合搅拌,加入丁基三苯基溴化膦和甲苯磺酰肼反应,得到中间体;S1: 2-(methacrylate)ethyl 3,5-diaminobenzoic acid, 2-methoxy-4-vinylphenol and N,N-dimethylformamide are mixed and stirred, and butyltriphenylphosphine bromide and toluenesulfonyl hydrazide are added to react to obtain an intermediate;

S2将中间体、水、烷基酚聚氧乙烯聚氧丙烯醚、丙烯腈、有机酸、乙二胺四乙酸四钠盐、正十二烷基叔硫醇、十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,搅拌,再加入丁二烯和偶氮二异丁腈继续反应,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到改性丁腈橡胶。S2: The intermediate, water, alkylphenol polyoxyethylene polyoxypropylene ether, acrylonitrile, organic acid, tetrasodium ethylenediaminetetraacetic acid, n-dodecyl tertiary mercaptan, and sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred, butadiene and azobisisobutyronitrile are added to continue the reaction, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain modified nitrile rubber.

进一步的,所述改性丁腈橡胶的制备方法如下:Further, the preparation method of the modified nitrile rubber is as follows:

S1将3-5重量份2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸、5-10重量份2-甲氧基-4-乙烯基苯酚与70-130重量份N,N-二甲基甲酰胺混合,在400-800rpm下搅拌8-15min,加入5-10重量份丁基三苯基溴化膦和4-6重量份甲苯磺酰肼,在40-50℃下反应5-8h,减压蒸馏去除溶剂,得到中间体;S1: 3-5 parts by weight of 2-(methacrylate)ethyl 3,5-diaminobenzoic acid, 5-10 parts by weight of 2-methoxy-4-vinylphenol and 70-130 parts by weight of N,N-dimethylformamide are mixed, stirred at 400-800 rpm for 8-15 min, 5-10 parts by weight of butyltriphenylphosphonium bromide and 4-6 parts by weight of toluenesulfonylhydrazide are added, reacted at 40-50° C. for 5-8 h, and the solvent is removed by distillation under reduced pressure to obtain an intermediate;

S2将4-6重量份中间体、60-120重量份水、1-3重量份烷基酚聚氧乙烯聚氧丙烯醚、10-25重量份丙烯腈、10-25重量份甲基丙烯酸、0.1-0.3重量份乙二胺四乙酸四钠盐、2-5重量份正十二烷基叔硫醇、2-5重量份十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,在200-600rpm、40-50℃下搅拌20-40min,再加入20-40重量份丁二烯和0.5-2重量份偶氮二异丁腈,继续反应40-80min,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到改性丁腈橡胶。S2: 4-6 parts by weight of the intermediate, 60-120 parts by weight of water, 1-3 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 10-25 parts by weight of acrylonitrile, 10-25 parts by weight of methacrylic acid, 0.1-0.3 parts by weight of ethylenediaminetetraacetic acid tetrasodium salt, 2-5 parts by weight of n-dodecyl tertiary mercaptan, and 2-5 parts by weight of sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred at 200-600rpm and 40-50°C for 20-40min, then 20-40 parts by weight of butadiene and 0.5-2 parts by weight of azobisisobutyronitrile are added, the reaction is continued for 40-80min, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain a modified nitrile rubber.

所述有机酸为2-乙基丙烯酸、甲基丙烯酸、丙烯酸中的至少一种。The organic acid is at least one of 2-ethylacrylic acid, methacrylic acid and acrylic acid.

所述耐油聚氯乙烯电缆采用如下方法制备而成:将聚氯乙烯60-120份、羧基丁基橡胶或改性丁腈橡胶15-30份、苯乙烯系弹性体10-30份、苯胺甲醛树脂5-12份、乙烯基三甲氧基硅烷5-12份、抗氧剂2-4份、硫化剂1-3份、马来酸酐-苯乙烯共聚物5-12份、硬脂酸锌1-3份、癸二酸二辛酯2-5份、液体石蜡5-10份、白炭黑5-15份和氧化锌10-30份混合搅拌,在120-150℃下混炼8-15min,挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。The oil-resistant polyvinyl chloride cable is prepared by the following method: 60-120 parts of polyvinyl chloride, 15-30 parts of carboxybutyl rubber or modified nitrile rubber, 10-30 parts of styrene elastomer, 5-12 parts of aniline formaldehyde resin, 5-12 parts of vinyl trimethoxysilane, 2-4 parts of antioxidant, 1-3 parts of vulcanizing agent, 5-12 parts of maleic anhydride-styrene copolymer, 1-3 parts of zinc stearate, 2-5 parts of dioctyl sebacate, 5-10 parts of liquid paraffin, 5-15 parts of white carbon black and 10-30 parts of zinc oxide are mixed and stirred, kneaded at 120-150° C. for 8-15 minutes, extruded and formed, and coated on the surface of the conductor to obtain the oil-resistant polyvinyl chloride cable.

本发明的有益效果Beneficial Effects of the Invention

1、本发明提供一种耐油聚氯乙烯电缆,通过各物质之间的作用有效克服聚氯乙烯难塑化,制成品的冲击强度低、韧性表现较差、耐油性能不佳等缺陷,扩大了在电力电缆套管中应用,尤其是用在耐油电缆套管中,有效降低电缆在储存和使用中出现开裂等缺陷。1. The present invention provides an oil-resistant polyvinyl chloride cable, which effectively overcomes the defects of polyvinyl chloride being difficult to plasticize, having low impact strength, poor toughness, and poor oil resistance of the finished product through the interaction between various substances, expands the application in power cable sheaths, especially in oil-resistant cable sheaths, and effectively reduces defects such as cracking of cables during storage and use.

2、本发明通过对羧基丁晴橡胶进行了进一步的改性处理,并配合纳米填料的相互作用,大幅度的提高了聚氯乙烯电缆材料的性能,尤其是耐油性能、耐磨、机械性能均具有大幅度的提高,从而显著的提高了电缆的工作寿命。2. The present invention further modifies the carboxylated nitrile rubber and cooperates with the interaction of nanofillers to greatly improve the performance of polyvinyl chloride cable materials, especially the oil resistance, wear resistance and mechanical properties, thereby significantly improving the service life of the cable.

3、本发明提供一种改性丁腈橡胶的制备方法,通过以2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸和2-甲氧基-4-乙烯基苯酚反应,得到超分子聚合物作为改性剂,利用超分子聚合物中的氨基和羟基与羧基丁腈橡胶羧基反应,羧基与氨基或羟基缩合形成酰胺键或酯基,得到的改性丁腈橡胶,改性后的羧基丁腈橡胶受力拉伸时,超分子聚合物自身的羟基和氨基之间的氢键以及超分子聚合物与羧基丁腈橡胶之间的氢键优先于共价键断裂耗散能量,氢键的断裂会避免共价键交联的羧基丁腈橡胶因应力集中而过早地被破坏,从而显著提升羧基丁腈橡胶的强度和韧性,同时还能提高耐油性能和耐磨性能。3. The present invention provides a method for preparing a modified nitrile rubber, wherein a supramolecular polymer is obtained as a modifier by reacting 2-(methacrylate)ethyl 3,5-diaminobenzoic acid and 2-methoxy-4-vinylphenol, and an amino group and a hydroxyl group in the supramolecular polymer are reacted with a carboxyl group of a carboxyl nitrile rubber, and the carboxyl group condenses with the amino group or the hydroxyl group to form an amide bond or an ester group to obtain a modified nitrile rubber. When the modified carboxyl nitrile rubber is stretched, hydrogen bonds between the hydroxyl group and the amino group of the supramolecular polymer itself and hydrogen bonds between the supramolecular polymer and the carboxyl nitrile rubber break and dissipate energy before covalent bonds break. The breaking of hydrogen bonds prevents the covalently cross-linked carboxyl nitrile rubber from being destroyed prematurely due to stress concentration, thereby significantly improving the strength and toughness of the carboxyl nitrile rubber, and also improving the oil resistance and wear resistance.

具体实施方式Detailed ways

下面结合具体实施方式对本发明的上述发明内容作进一步的详细描述,但不应将此理解为本发明上述主题的范围仅限于下述实施例。The above content of the present invention is further described in detail below in conjunction with specific implementation modes, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments.

本申请中部分原料的介绍:Introduction of some raw materials in this application:

聚氯乙烯购于东莞市樟木头恒泰塑胶原料经营部,牌号DMDA-8008。Polyvinyl chloride was purchased from Hengtai Plastic Raw Materials Business Department in Zhangmutou, Dongguan City, with the brand name DMDA-8008.

市售的丁腈橡胶购于衡水利尔科技有限公司,牌号FGGF43。Commercially available nitrile rubber was purchased from Hengshui Lier Technology Co., Ltd., with the brand name FGGF43.

苯乙烯系弹性体购于广东鼎信聚合科技有限公司,牌号D-1161JSP。Styrene elastomer was purchased from Guangdong Dingxin Polymer Technology Co., Ltd., brand D-1161JSP.

苯胺甲醛树脂购于东莞太洋新材料科技有限公司,型号TY-8912。Aniline formaldehyde resin was purchased from Dongguan Taiyang New Material Technology Co., Ltd., model TY-8912.

烷基酚聚氧乙烯聚氧丙烯醚购于南通奥宸化工有限公司,型号NPE-108。Alkylphenol polyoxyethylene polyoxypropylene ether was purchased from Nantong Aochen Chemical Co., Ltd., model NPE-108.

实施例1Example 1

一种耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下重量份原料组成:聚氯乙烯80份、丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份。An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 20 parts of nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropyl benzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide.

所述丁腈橡胶为市售的丁腈橡胶。The nitrile rubber is commercially available nitrile rubber.

所述导体为铜。The conductor is copper.

所述耐油聚氯乙烯电缆采用如下方法制备而成:将聚氯乙烯80份、丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份混合搅拌,在135℃下混炼10min,挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。The oil-resistant polyvinyl chloride cable is prepared by the following method: 80 parts of polyvinyl chloride, 20 parts of nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropylbenzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide are mixed and stirred, kneaded at 135° C. for 10 minutes, extruded and formed, and coated on the surface of the conductor to obtain the oil-resistant polyvinyl chloride cable.

实施例2Example 2

一种耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下重量份原料组成:聚氯乙烯80份、羧基丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份。An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 20 parts of carboxylated nitrile rubber, 20 parts of styrene-based elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropyl benzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide.

所述羧基丁腈橡胶的制备方法如下:将70重量份水、2重量份烷基酚聚氧乙烯聚氧丙烯醚、15重量份丙烯腈、20重量份甲基丙烯酸、0.15重量份乙二胺四乙酸四钠盐、3.5重量份正十二烷基叔硫醇、2.5重量份十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,在400rpm、45℃下搅拌30min,再加入30重量份丁二烯和1重量份偶氮二异丁腈,继续反应50min,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到所述羧基丁腈橡胶。The preparation method of the carboxylated nitrile rubber is as follows: 70 parts by weight of water, 2 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 15 parts by weight of acrylonitrile, 20 parts by weight of methacrylic acid, 0.15 parts by weight of ethylenediaminetetraacetic acid tetrasodium salt, 3.5 parts by weight of n-dodecyl tertiary mercaptan, and 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized and replaced with nitrogen three times, stirred at 400 rpm and 45° C. for 30 minutes, then 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile are added, the reaction is continued for 50 minutes, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain the carboxylated nitrile rubber.

所述导体为铜。The conductor is copper.

所述耐油聚氯乙烯电缆采用如下方法制备而成:将聚氯乙烯80份、羧基丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份混合搅拌,在135℃下混炼10min,挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。The oil-resistant polyvinyl chloride cable is prepared by the following method: 80 parts of polyvinyl chloride, 20 parts of carboxyl nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropylbenzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide are mixed and stirred, kneaded at 135° C. for 10 minutes, extruded and formed, and coated on the surface of the conductor to obtain the oil-resistant polyvinyl chloride cable.

实施例3Example 3

一种耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下重量份原料组成:聚氯乙烯80份、改性丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂1010 3份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份。An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 3 parts of antioxidant 1010, 2 parts of di-tert-butyl peroxy isopropyl benzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide.

所述改性丁腈橡胶的制备方法如下:The preparation method of the modified nitrile rubber is as follows:

S1将4重量份2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸、8重量份2-甲氧基-4-乙烯基苯酚与80重量份N,N-二甲基甲酰胺混合,在600rpm下搅拌10min,加入8重量份丁基三苯基溴化膦和6重量份甲苯磺酰肼,在45℃下反应6h,减压蒸馏去除溶剂,得到中间体;S1: 4 parts by weight of 2-(methacrylate)ethyl 3,5-diaminobenzoic acid, 8 parts by weight of 2-methoxy-4-vinylphenol and 80 parts by weight of N,N-dimethylformamide were mixed, stirred at 600 rpm for 10 min, 8 parts by weight of butyltriphenylphosphonium bromide and 6 parts by weight of toluenesulfonylhydrazide were added, reacted at 45° C. for 6 h, and the solvent was removed by distillation under reduced pressure to obtain an intermediate;

S2将4.5重量份中间体、70重量份水、2重量份烷基酚聚氧乙烯聚氧丙烯醚、15重量份丙烯腈、20重量份甲基丙烯酸、0.15重量份乙二胺四乙酸四钠盐、3.5重量份正十二烷基叔硫醇、2.5重量份十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,在400rpm、45℃下搅拌30min,再加入30重量份丁二烯和1重量份偶氮二异丁腈,继续反应50min,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到改性丁腈橡胶。S2: 4.5 parts by weight of the intermediate, 70 parts by weight of water, 2 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 15 parts by weight of acrylonitrile, 20 parts by weight of methacrylic acid, 0.15 parts by weight of tetrasodium ethylenediaminetetraacetic acid, 3.5 parts by weight of n-dodecyl tertiary mercaptan, and 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred at 400 rpm and 45° C. for 30 minutes, then 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile are added, the reaction is continued for 50 minutes, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain a modified nitrile rubber.

所述导体为铜。The conductor is copper.

所述耐油聚氯乙烯电缆采用如下方法制备而成:将聚氯乙烯80份、改性丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份混合搅拌,在135℃下混炼10min,挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。The oil-resistant polyvinyl chloride cable is prepared by the following method: 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropylbenzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide are mixed and stirred, kneaded at 135° C. for 10 minutes, extruded and formed, and coated on the surface of the conductor to obtain the oil-resistant polyvinyl chloride cable.

实施例4Example 4

一种耐油聚氯乙烯电缆,包括导体和护套层,所述护套层由以下重量份原料组成:聚氯乙烯80份、改性丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份。An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of the following raw materials in parts by weight: 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropyl benzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide.

所述改性丁腈橡胶的制备方法如下:The preparation method of the modified nitrile rubber is as follows:

S1将4重量份2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸、8重量份2-甲氧基-4-乙烯基苯酚与80重量份N,N-二甲基甲酰胺混合,在600rpm下搅拌10min,加入8重量份丁基三苯基溴化膦和6重量份甲苯磺酰肼,在45℃下反应6h,减压蒸馏去除溶剂,得到中间体;S1: 4 parts by weight of 2-(methacrylate)ethyl 3,5-diaminobenzoic acid, 8 parts by weight of 2-methoxy-4-vinylphenol and 80 parts by weight of N,N-dimethylformamide were mixed, stirred at 600 rpm for 10 min, 8 parts by weight of butyltriphenylphosphonium bromide and 6 parts by weight of toluenesulfonylhydrazide were added, reacted at 45° C. for 6 h, and the solvent was removed by distillation under reduced pressure to obtain an intermediate;

S2将4.5重量份中间体、70重量份水、2重量份烷基酚聚氧乙烯聚氧丙烯醚、15重量份丙烯腈、0.15重量份乙二胺四乙酸四钠盐、3.5重量份正十二烷基叔硫醇、2.5重量份十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,在400rpm、45℃下搅拌30min,再加入30重量份丁二烯和1重量份偶氮二异丁腈,继续反应50min,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到改性丁腈橡胶。S2: 4.5 parts by weight of the intermediate, 70 parts by weight of water, 2 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 15 parts by weight of acrylonitrile, 0.15 parts by weight of tetrasodium ethylenediaminetetraacetic acid, 3.5 parts by weight of n-dodecyl tertiary mercaptan, and 2.5 parts by weight of sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized and replaced with nitrogen three times, stirred at 400 rpm and 45° C. for 30 minutes, then 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile are added, the reaction is continued for 50 minutes, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain a modified nitrile rubber.

所述导体为铜。The conductor is copper.

所述耐油聚氯乙烯电缆采用如下方法制备而成:将聚氯乙烯80份、改性丁腈橡胶20份、苯乙烯系弹性体20份、苯胺甲醛树脂10份、乙烯基三甲氧基硅烷8份、抗氧剂10103份、双叔丁基过氧异丙基苯2份、马来酸酐-苯乙烯共聚物10份、硬脂酸锌2份、癸二酸二辛酯3份、液体石蜡7份、白炭黑10份和氧化锌20份混合搅拌,在135℃下混炼10min,挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。The oil-resistant polyvinyl chloride cable is prepared by the following method: 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of antioxidant, 2 parts of di-tert-butyl peroxy isopropylbenzene, 10 parts of maleic anhydride-styrene copolymer, 2 parts of zinc stearate, 3 parts of dioctyl sebacate, 7 parts of liquid paraffin, 10 parts of white carbon black and 20 parts of zinc oxide are mixed and stirred, kneaded at 135° C. for 10 minutes, extruded and formed, and coated on the surface of the conductor to obtain the oil-resistant polyvinyl chloride cable.

测试例1Test Example 1

磨损性能测试:采用国家标准GB/T3960-2016《塑料滑动摩擦磨损试验方法》对实施例1-4制备得到的耐油聚氯乙烯电缆进行测试,磨损率越低,耐磨性能越好。每组设置5个平行试样,取平均值,结果见表1。Wear performance test: The oil-resistant polyvinyl chloride cables prepared in Examples 1-4 were tested using the national standard GB/T3960-2016 "Plastic Sliding Friction Wear Test Method". The lower the wear rate, the better the wear resistance. Five parallel samples were set in each group, and the average value was taken. The results are shown in Table 1.

表1磨损性能测试结果Table 1 Wear performance test results

磨损率,%Wear rate,% 实施例1Example 1 0.570.57 实施例2Example 2 0.480.48 实施例3Example 3 0.120.12 实施例4Example 4 0.290.29

测试例2Test Example 2

耐油性能测试:采用国家标准GB/T1690-2010《硫化橡胶或热塑性橡胶耐液体试验方法》进行测试,将实施例1-4中的耐油聚氯乙烯电缆料用注塑机注塑成型,试样为I型,试样尺寸大小为25mm*50mm*2mm,油类为液体B(30%甲苯,70%异辛烷),在温度为23℃条件下浸泡168h,测试质量变化率、拉伸强度和断裂伸长率,每组设置5个平行试样,取平均值,结果见表2。Oil resistance test: The national standard GB/T1690-2010 "Test method for liquid resistance of vulcanized rubber or thermoplastic rubber" was used for testing. The oil-resistant polyvinyl chloride cable material in Example 1-4 was injection molded by an injection molding machine. The sample was type I, the sample size was 25mm*50mm*2mm, and the oil was liquid B (30% toluene, 70% isooctane). It was immersed for 168h at a temperature of 23°C, and the mass change rate, tensile strength and elongation at break were tested. Five parallel samples were set in each group, and the average value was taken. The results are shown in Table 2.

表2力学性能测试结果Table 2 Mechanical properties test results

从上述结果可知,本发明制备得到的耐油聚氯乙烯电缆的耐油性能和耐磨以及机械性能良好,从实施例1-2可知,羧基丁腈橡胶的极性较高,增大了与聚氯乙烯、基体等极性材料的相容性,并使耐油性能进一步提升;同时,羧基的引入也提高了材料的拉伸强度,特别是提高了高温下的拉伸强度,可以有效提高电缆在安装和使用过程中的柔韧性和耐久性。From the above results, it can be seen that the oil-resistant polyvinyl chloride cable prepared by the present invention has good oil resistance, wear resistance and mechanical properties. From Examples 1-2, it can be seen that the polarity of the carboxyl nitrile rubber is relatively high, which increases the compatibility with polar materials such as polyvinyl chloride and matrix, and further improves the oil resistance; at the same time, the introduction of carboxyl groups also improves the tensile strength of the material, especially the tensile strength at high temperatures, which can effectively improve the flexibility and durability of the cable during installation and use.

从实施例2-4可知,本发明通过对羧基丁晴橡胶进行了进一步的改性处理,并配合纳米填料的相互作用,大幅度的提高了聚氯乙烯电缆材料的性能,尤其是耐油性能、耐磨、机械性能均具有大幅度的提高,从而显著的提高了电缆的工作寿命。原因是以2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸和2-甲氧基-4-乙烯基苯酚反应,得到超分子聚合物作为改性剂,超分子聚合物包括基于多种分子间相互作用以及它们的协同作用或多重作用形成的聚合物,利用超分子聚合物中的氨基和羟基与羧基丁腈橡胶羧基反应,羧基与氨基或羟基缩合形成酰胺键或酯基,得到的改性丁腈橡胶,改性后的羧基丁腈橡胶受力拉伸时,超分子聚合物自身的羟基和氨基之间的氢键以及超分子聚合物与羧基丁腈橡胶之间的氢键优先于共价键断裂耗散能量,氢键的断裂会避免共价键交联的羧基丁腈橡胶因应力集中而过早地被破坏,从而显著提升羧基丁腈橡胶的强度和韧性,同时还能提高耐油性能和耐磨性能。It can be seen from Examples 2-4 that the present invention further modifies the carboxylated nitrile rubber and cooperates with the interaction of nanofillers to greatly improve the performance of the polyvinyl chloride cable material, especially the oil resistance, wear resistance and mechanical properties, thereby significantly increasing the service life of the cable. The reason is that 2-(methacrylate)ethyl 3,5-diaminobenzoic acid and 2-methoxy-4-vinylphenol are reacted to obtain a supramolecular polymer as a modifier. The supramolecular polymer includes polymers formed based on multiple intermolecular interactions and their synergistic or multiple effects. The amino group and hydroxyl group in the supramolecular polymer react with the carboxyl group of carboxyl nitrile rubber. The carboxyl group condenses with the amino group or the hydroxyl group to form an amide bond or an ester group to obtain a modified nitrile rubber. When the modified carboxyl nitrile rubber is stretched, the hydrogen bonds between the hydroxyl group and the amino group of the supramolecular polymer itself and the hydrogen bonds between the supramolecular polymer and the carboxyl nitrile rubber break before the covalent bonds break to dissipate energy. The breaking of the hydrogen bonds will prevent the covalently cross-linked carboxyl nitrile rubber from being destroyed prematurely due to stress concentration, thereby significantly improving the strength and toughness of the carboxyl nitrile rubber, while also improving the oil resistance and wear resistance.

Claims (8)

1.一种耐油聚氯乙烯电缆,包括导体和护套层,其特征在于,所述护套层由以下原料组成:聚氯乙烯、羧基丁基橡胶或改性丁腈橡胶、苯乙烯系弹性体、苯胺甲醛树脂、乙烯基三甲氧基硅烷、抗氧剂、硫化剂、马来酸酐-苯乙烯共聚物、硬脂酸锌、癸二酸二辛酯、液体石蜡、白炭黑和氧化锌。1. An oil-resistant polyvinyl chloride cable, comprising a conductor and a sheath layer, characterized in that the sheath layer is composed of the following raw materials: polyvinyl chloride, carboxybutyl rubber or modified nitrile rubber, styrene elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, antioxidant, vulcanizing agent, maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide. 2.如权利要求1所述的耐油聚氯乙烯电缆,其特征在于,所述硫化剂为双叔丁基过氧异丙基苯、过氧化二异丙苯、叔丁基苯酚甲醛树脂中的任一种。2. The oil-resistant polyvinyl chloride cable according to claim 1, characterized in that the vulcanizing agent is any one of di-tert-butyl peroxyisopropylbenzene, diisopropylbenzene peroxide, and tert-butylphenol formaldehyde resin. 3.如权利要求1所述的耐油聚氯乙烯电缆,其特征在于,所述抗氧剂为抗氧剂1010、抗氧剂168、抗氧剂1080、抗氧剂1076中的任一种。3. The oil-resistant polyvinyl chloride cable according to claim 1 is characterized in that the antioxidant is any one of antioxidant 1010, antioxidant 168, antioxidant 1080, and antioxidant 1076. 4.如权利要求1所述的耐油聚氯乙烯电缆,其特征在于,所述导体为铜、锌、铁中的任一种。4. The oil-resistant polyvinyl chloride cable according to claim 1, characterized in that the conductor is any one of copper, zinc and iron. 5.如权利要求1所述的耐油聚氯乙烯电缆,其特征在于,所述羧基丁腈橡胶的制备方法如下:将水、烷基酚聚氧乙烯聚氧丙烯醚、丙烯腈、有机酸、乙二胺四乙酸四钠盐、正十二烷基叔硫醇、十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,搅拌,再加入丁二烯和偶氮二异丁腈继续反应,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到羧基丁腈橡胶。5. The oil-resistant polyvinyl chloride cable as claimed in claim 1 is characterized in that the preparation method of the carboxylated nitrile rubber is as follows: water, alkylphenol polyoxyethylene polyoxypropylene ether, acrylonitrile, organic acid, tetrasodium salt of ethylenediaminetetraacetic acid, n-dodecyl tertiary mercaptan, and sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred, butadiene and azobisisobutyronitrile are added to continue the reaction, cooled to room temperature, and the solvent is removed by reduced pressure distillation, washed, and dried to obtain the carboxylated nitrile rubber. 6.如权利要求1所述的耐油聚氯乙烯电缆,其特征在于,所述改性丁腈橡胶的制备方法如下:6. The oil-resistant polyvinyl chloride cable according to claim 1, characterized in that the preparation method of the modified nitrile rubber is as follows: S1将2-(甲基丙烯酸)乙酯3,5-二氨基苯甲酸、2-甲氧基-4-乙烯基苯酚与N,N-二甲基甲酰胺混合搅拌,加入丁基三苯基溴化膦和甲苯磺酰肼反应,得到中间体;S1: 2-(methacrylate)ethyl 3,5-diaminobenzoic acid, 2-methoxy-4-vinylphenol and N,N-dimethylformamide are mixed and stirred, and butyltriphenylphosphine bromide and toluenesulfonyl hydrazide are added to react to obtain an intermediate; S2将中间体、水、烷基酚聚氧乙烯聚氧丙烯醚、丙烯腈、有机酸、乙二胺四乙酸四钠盐、正十二烷基叔硫醇、十二烷基联苯醚二磺酸钠混合,抽真空、氮气置换3次,搅拌,再加入丁二烯和偶氮二异丁腈继续反应,冷却至室温,经过减压蒸馏除溶剂、洗涤、干燥得到改性丁腈橡胶。S2: The intermediate, water, alkylphenol polyoxyethylene polyoxypropylene ether, acrylonitrile, organic acid, tetrasodium ethylenediaminetetraacetic acid, n-dodecyl tertiary mercaptan, and sodium dodecyl diphenyl ether disulfonate are mixed, vacuumized, replaced with nitrogen three times, stirred, butadiene and azobisisobutyronitrile are added to continue the reaction, cooled to room temperature, the solvent is removed by reduced pressure distillation, washed, and dried to obtain modified nitrile rubber. 7.如权利要求5或6所述的耐油聚氯乙烯电缆,其特征在于,所述有机酸为2-乙基丙烯酸、甲基丙烯酸、丙烯酸中的至少一种。7. The oil-resistant polyvinyl chloride cable according to claim 5 or 6, characterized in that the organic acid is at least one of 2-ethylacrylic acid, methacrylic acid and acrylic acid. 8.如权利要求1-7任一项所述的耐油聚氯乙烯电缆的制备方法,其特征在于,将聚氯乙烯、羧基丁基橡胶或改性丁腈橡胶、苯乙烯系弹性体、苯胺甲醛树脂、乙烯基三甲氧基硅烷、抗氧剂、硫化剂、马来酸酐-苯乙烯共聚物、硬脂酸锌、癸二酸二辛酯、液体石蜡、白炭黑和氧化锌混合搅拌,混炼挤出成型,包覆于导体表面,得到耐油聚氯乙烯电缆。8. The method for preparing an oil-resistant polyvinyl chloride cable according to any one of claims 1 to 7, characterized in that polyvinyl chloride, carboxybutyl rubber or modified nitrile rubber, styrene-based elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, antioxidant, vulcanizing agent, maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide are mixed and stirred, kneaded and extruded, and coated on the surface of a conductor to obtain an oil-resistant polyvinyl chloride cable.
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