CN118146598B - Oil-resistant polyvinyl chloride cable - Google Patents
Oil-resistant polyvinyl chloride cable Download PDFInfo
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- CN118146598B CN118146598B CN202410405772.7A CN202410405772A CN118146598B CN 118146598 B CN118146598 B CN 118146598B CN 202410405772 A CN202410405772 A CN 202410405772A CN 118146598 B CN118146598 B CN 118146598B
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators 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
- H01B3/44—Insulators 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
- H01B3/443—Insulators 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
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Abstract
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。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。本发明通过在护套层中添加改性丁腈橡胶，有效解决了聚氯乙烯电缆的耐油耐性和耐磨以及机械性能不佳，有效提升耐油聚氯乙烯电缆的强度和韧性，同时还能提高耐油性能和耐磨性能。The present invention relates to the field of cable technology, and in particular to an oil-resistant polyvinyl chloride cable. The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, and 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. The present invention effectively solves the poor oil resistance and wear resistance and mechanical properties of polyvinyl chloride cables by adding modified nitrile rubber to the sheath layer, effectively improves the strength and toughness of the oil-resistant polyvinyl chloride cable, and can also improve the oil resistance and wear resistance.
Description
Technical Field
The invention relates to the technical field of cables, in particular to an oil-resistant polyvinyl chloride cable.
Background
Polyvinyl chloride has good insulating property, mechanical property, processability and the like, and is widely used as an insulating material and a sheath material of wires and cables. However, the hardness of the polyvinyl chloride is high, and in order to prepare the polyvinyl chloride soft plastic for the electric wires and cables, a plasticizer is generally added into the polyvinyl chloride to improve the plasticity of the polyvinyl chloride soft plastic, so that the polyvinyl chloride plastic is ensured to have certain softness. Polyvinyl chloride is a modified material obtained by chloridizing polyvinyl chloride, and the chlorine content is higher than that of polyvinyl chloride resin, generally more than 65%. The improvement of chlorine content and polarity increase gives a series of excellent properties. Compared with polyvinyl chloride, the PVC has high strength, heat resistance, corrosion resistance, small thermal expansion coefficient, flame resistance and low oxygen transmittance, the high-voltage and ultra-high voltage cable laying sleeve can meet the requirements of heat resistance, flame retardance, compression resistance, construction and the like, and is a material with excellent performance. However, polyvinyl chloride is difficult to plasticize, and the impact strength of the finished product is low, so that the polyvinyl chloride material is required to be modified according to specific technical requirements of processability, impact performance and the like in the application of the polyvinyl chloride material in power cable bushings, especially in large-caliber power cable bushings.
The Chinese patent CN116814021B discloses a high-strength wear-resistant cable which consists of a bunched cable core and a wear-resistant sheath, wherein the wear-resistant sheath comprises, 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 a temperature-resistant reinforcing agent, 7-11 parts of a wear-resistant filler, 3-5 parts of a lubricant, 5-8 parts of a toughening agent and 0.2-0.3 part of an antioxidant. Although the invention effectively solves the wear resistance of the cable, the cable in the invention has poor oil resistance and mechanical strength to be improved.
Disclosure of Invention
Aiming at the defects of the mechanical strength and oil resistance of the cable material in the prior art, the invention provides an oil-resistant polyvinyl chloride cable.
In order to solve the technical problems, the invention adopts the following technical scheme:
the oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer is composed of polyvinyl chloride, carboxyl butyl rubber or modified nitrile rubber, a styrene elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, an antioxidant, a vulcanizing agent, a maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide.
Preferably, the oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer comprises, by weight, 60-120 parts of polyvinyl chloride, 15-30 parts of carboxyl butyl rubber or modified nitrile rubber, 10-30 parts of a styrene elastomer, 5-12 parts of an aniline formaldehyde resin, 5-12 parts of vinyl trimethoxy silane, 2-4 parts of an antioxidant, 1-3 parts of a vulcanizing agent, 5-12 parts of a 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.
The conductor is any one of copper, zinc and iron.
The vulcanizing agent is any one of di-tert-butyl peroxyisopropyl benzene, dicumyl peroxide and tert-butylphenol formaldehyde resin.
The antioxidant is any one of antioxidant 1010, antioxidant 168, antioxidant 1080 and antioxidant 1076.
The polyvinyl chloride is difficult to plasticize, and the finished product has low impact strength, poor toughness and poor oil resistance, is applied to the power cable sleeve, especially to the oil-resistant cable sleeve, has short service life due to poor oil resistance, processability, impact performance and the like, and is easy to cause the defects of cracking and the like of the cable in storage and use.
The nitrile rubber has unsaturated double bond and cyano in molecular structure, so that the nitrile rubber has the advantages of good oil resistance, good wear resistance and strong adhesive force, and is widely used for preparing various oil-resistant rubber products. The carboxyl nitrile rubber has higher polarity, increases the compatibility with polar materials such as polyvinyl chloride, a matrix and the like, further improves the oil resistance, and simultaneously improves the tensile strength of the material, particularly the tensile strength at high temperature due to the introduction of carboxyl. The invention aims at adding the carboxyl nitrile rubber with high oil resistance, wear resistance and adhesion, which can improve the compatibility of the nitrile rubber and a raw material matrix and can improve the oil resistance of a polyvinyl chloride cable material to a certain extent, and the carboxyl nitrile rubber has good plasticity and elasticity in certain aspects like polyvinyl chloride, which can affect the flexibility and durability of the cable during installation and use.
The preparation method of the carboxylated nitrile rubber comprises the steps of mixing 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times by nitrogen, stirring for 20-40min at 200-600rpm and 40-50 ℃, adding 20-40 parts by weight of butadiene and 0.5-2 parts by weight of azodiisobutyronitrile, continuing to react for 40-80min, cooling to room temperature, removing solvent by reduced pressure distillation, washing and drying to obtain the carboxylated nitrile rubber.
The carboxyl nitrile rubber has relatively poor properties, especially oil resistance and dimensional stability, due to the characteristics of incapability of crystallization, small intermolecular acting force of the rubber and the like, and the service life of the cable material prepared by taking the carboxyl nitrile rubber as a base material is greatly shortened, so that, according to the invention, the carboxyl nitrile rubber is further modified and is matched with the interaction of the nano filler, so that the performance of the polyvinyl chloride cable material, particularly the oil resistance, the wear resistance and the mechanical performance are greatly improved, and the service life of the cable is remarkably prolonged.
According to the invention, the carboxyl nitrile rubber is further modified, wherein 2- (methacrylic acid) ethyl 3, 5-diaminobenzoic acid and 2-methoxy-4-vinylphenol react to obtain a supermolecular polymer serving as a modifier, the supermolecular polymer comprises a polymer formed based on the interaction among various molecules and the synergistic effect or multiple effects of the intermolecular interactions, amino groups and hydroxyl groups in the supermolecular polymer react with carboxyl groups of the carboxyl nitrile rubber, carboxyl groups are condensed with amino groups or hydroxyl groups to form amide bonds or ester groups, and the modified nitrile rubber is obtained.
Preferably, the preparation method of the modified nitrile rubber comprises the following steps:
S1, mixing and stirring 2- (methacrylic acid) ethyl 3, 5-diaminobenzoic acid, 2-methoxy-4-vinylphenol and N, N-dimethylformamide, and adding butyl triphenylphosphine bromide and toluene sulfonyl hydrazine for reaction to obtain an intermediate;
S2, mixing an intermediate, water, alkylphenol polyoxyethylene polyoxypropylene ether, acrylonitrile, organic acid, ethylene diamine tetraacetic acid tetrasodium salt, n-dodecyl tertiary mercaptan and sodium dodecyl diphenyl ether disulfonate, vacuumizing, replacing nitrogen for 3 times, stirring, adding butadiene and azodiisobutyronitrile for continuous reaction, cooling to room temperature, and obtaining the modified nitrile rubber through reduced pressure distillation to remove solvent, washing and drying.
Further, the preparation method of the modified nitrile rubber comprises the following steps:
s1, mixing 3-5 parts by weight of 2- (methacrylic acid) 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, stirring for 8-15min at 400-800rpm, adding 5-10 parts by weight of butyltriphenylphosphine bromide and 4-6 parts by weight of tosyl hydrazide, reacting for 5-8h at 40-50 ℃, and distilling under reduced pressure to remove a solvent to obtain an intermediate;
S2, mixing 4-6 parts by weight of an 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times by nitrogen, stirring for 20-40min at 200-600rpm and 40-50 ℃, adding 20-40 parts by weight of butadiene and 0.5-2 parts by weight of azodiisobutyronitrile, continuing to react for 40-80min, cooling to room temperature, removing solvent by reduced pressure distillation, washing and drying to obtain the modified nitrile rubber.
The organic acid is at least one of 2-ethyl acrylic acid, methacrylic acid and acrylic acid.
The oil-resistant polyvinyl chloride cable is prepared by mixing and stirring 60-120 parts of polyvinyl chloride, 15-30 parts of carboxyl butyl 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, mixing for 8-15min at 120-150 ℃, extruding and molding, and coating the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
The beneficial effects of the invention are that
1. The invention provides an oil-resistant polyvinyl chloride cable, which effectively overcomes the defects of difficult plasticization of polyvinyl chloride, low impact strength, poor toughness performance, poor oil resistance and the like of finished products, expands the application in power cable bushings, particularly in oil-resistant cable bushings, and effectively reduces the defects of cracking and the like of cables in storage and use.
2. According to the invention, the carboxyl nitrile rubber is further modified and is matched with the interaction of the nano filler, so that the performance of the polyvinyl chloride cable material, particularly the oil resistance, the wear resistance and the mechanical performance are greatly improved, and the service life of the cable is remarkably prolonged.
3. The invention provides a preparation method of modified nitrile rubber, which is characterized in that 2- (methacrylic acid) ethyl 3, 5-diaminobenzoic acid and 2-methoxy-4-vinylphenol are reacted to obtain a supermolecular polymer as a modifier, amino and hydroxyl in the supermolecular polymer are reacted with carboxyl of carboxyl nitrile rubber, carboxyl and amino or hydroxyl are condensed to form an amide bond or an ester group, and the modified nitrile rubber is obtained.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Introduction of partial raw materials in the application:
Polyvinyl chloride is purchased from Dongguan camphor wood Hengtai plastic raw material warp barrage, brand DMDA-8008.
The commercially available nitrile rubber is available from Hendel technology Co., ltd., trade name FGGF and 43.
The styrene elastomer is purchased from Guangdong Dingxin polymerization technology Co., ltd, and has the brand name D-1161JSP.
The aniline formaldehyde resin is purchased from Dongguan pacific new material science and technology Co., ltd, model TY-8912.
Alkylphenol polyoxyethylene polyoxypropylene ether was purchased from Nantong Alrod chemical Co., ltd., model NPE-108.
Example 1
The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer comprises, by weight, 80 parts of polyvinyl chloride, 20 parts of nitrile rubber, 20 parts of a styrene elastomer, 10 parts of an aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of an antioxidant, 2 parts of di-tert-butyl peroxyisopropyl benzene, 10 parts of a 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.
The nitrile rubber is commercially available nitrile rubber.
The conductor is copper.
The oil-resistant polyvinyl chloride cable is prepared by mixing and stirring 80 parts of polyvinyl chloride, 20 parts of nitrile rubber, 20 parts of a styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of an antioxidant, 2 parts of bis (tert-butyl) peroxyisopropyl 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, mixing for 10 minutes at 135 ℃, extruding and molding, and coating the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
Example 2
The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer comprises, by weight, 80 parts of polyvinyl chloride, 20 parts of carboxyl nitrile rubber, 20 parts of a styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of an antioxidant, 2 parts of di-tert-butyl peroxy isopropyl benzene, 10 parts of a 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.
The preparation method of the carboxylated nitrile rubber comprises the steps of mixing 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times with nitrogen, stirring for 30min at 400rpm and 45 ℃, adding 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile, continuing to react for 50min, cooling to room temperature, and obtaining the carboxylated nitrile rubber through reduced pressure distillation to remove solvent, washing and drying.
The conductor is copper.
The oil-resistant polyvinyl chloride cable is prepared by mixing and stirring 80 parts of polyvinyl chloride, 20 parts of carboxyl nitrile rubber, 20 parts of a styrene elastomer, 10 parts of aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of an antioxidant, 2 parts of di-tert-butyl peroxyisopropyl 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, mixing for 10 minutes at 135 ℃, extruding and molding, and coating the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
Example 3
The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer comprises, by weight, 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of a styrene elastomer, 10 parts of an aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 3 parts of an antioxidant 1010, 2 parts of bis-tert-butyl peroxyisopropyl benzene, 10 parts of a 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.
The preparation method of the modified nitrile rubber comprises the following steps:
S1, mixing 4 parts by weight of 2- (methacrylic acid) ethyl ester 3, 5-diaminobenzoic acid, 8 parts by weight of 2-methoxy-4-vinylphenol and 80 parts by weight of N, N-dimethylformamide, stirring for 10min at 600rpm, adding 8 parts by weight of butyltriphenylphosphine bromide and 6 parts by weight of toluene sulfonyl hydrazine, reacting for 6h at 45 ℃, and distilling off the solvent under reduced pressure to obtain an intermediate;
S2, mixing 4.5 parts by weight of an 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times with nitrogen, stirring for 30min at 400rpm and 45 ℃, adding 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile, continuing to react for 50min, cooling to room temperature, and obtaining the modified nitrile rubber through reduced pressure distillation to remove solvent, washing and drying.
The conductor is copper.
The oil-resistant polyvinyl chloride cable is prepared by mixing and stirring 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, mixing for 10 minutes at 135 ℃, extruding and molding, and coating the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
Example 4
The oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, wherein the sheath layer comprises, by weight, 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of a styrene elastomer, 10 parts of an aniline formaldehyde resin, 8 parts of vinyl trimethoxy silane, 10103 parts of an antioxidant, 2 parts of di-tert-butyl peroxyisopropyl benzene, 10 parts of a 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.
The preparation method of the modified nitrile rubber comprises the following steps:
S1, mixing 4 parts by weight of 2- (methacrylic acid) ethyl ester 3, 5-diaminobenzoic acid, 8 parts by weight of 2-methoxy-4-vinylphenol and 80 parts by weight of N, N-dimethylformamide, stirring for 10min at 600rpm, adding 8 parts by weight of butyltriphenylphosphine bromide and 6 parts by weight of toluene sulfonyl hydrazine, reacting for 6h at 45 ℃, and distilling off the solvent under reduced pressure to obtain an intermediate;
S2, mixing 4.5 parts by weight of an intermediate, 70 parts by weight of water, 2 parts by weight of alkylphenol polyoxyethylene polyoxypropylene ether, 15 parts by weight of acrylonitrile, 0.15 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times with nitrogen, stirring for 30min at 400rpm and 45 ℃, adding 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile, continuing to react for 50min, cooling to room temperature, removing a solvent by reduced pressure distillation, washing and drying to obtain the modified nitrile rubber.
The conductor is copper.
The oil-resistant polyvinyl chloride cable is prepared by mixing and stirring 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, mixing for 10 minutes at 135 ℃, extruding and molding, and coating the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
Test example 1
Abrasion performance test the oil-resistant polyvinyl chloride cable prepared in examples 1-4 is tested by adopting the national standard GB/T3960-2016 "Plastic sliding Friction abrasion test method", and the lower the abrasion rate is, the better the abrasion performance is. Each group was provided with 5 replicates and averaged, the results are shown in table 1.
TABLE 1 abrasion Performance test results
| Wear rate,% | |
| Example 1 | 0.57 |
| Example 2 | 0.48 |
| Example 3 | 0.12 |
| Example 4 | 0.29 |
Test example 2
The oil resistance test is carried out by adopting the national standard GB/T1690-2010 'vulcanized rubber or thermoplastic rubber liquid resistance test method', the oil-resistant polyvinyl chloride cable material in the examples 1-4 is injection molded by an injection molding machine, the sample is I-shaped, the size of the sample is 25mm x 50mm x 2mm, the oil is liquid B (30% toluene and 70% isooctane), the oil is soaked for 168 hours at the temperature of 23 ℃, the quality change rate, the tensile strength and the elongation at break are tested, 5 parallel samples are arranged in each group, and the average value is obtained, and the result is shown in the table 2.
TABLE 2 mechanical test results
From the results, the oil-resistant polyvinyl chloride cable prepared by the invention has good oil resistance, wear resistance and mechanical properties, and from examples 1-2, the carboxyl nitrile rubber has higher polarity, increases the compatibility with polar materials such as polyvinyl chloride and matrixes, and further improves the oil resistance, and meanwhile, the introduction of carboxyl improves the tensile strength of the materials, particularly the tensile strength at high temperature, so that the flexibility and durability of the cable in the installation and use processes can be effectively improved.
According to the invention, as shown in examples 2-4, the carboxyl nitrile rubber is further modified and is matched with the interaction of the nano filler, so that the performance of the polyvinyl chloride cable material, in particular the oil resistance, the wear resistance and the mechanical property are greatly improved, and the service life of the cable is remarkably prolonged. The method is characterized in that 2- (methacrylic acid) ethyl ester 3, 5-diaminobenzoic acid and 2-methoxy-4-vinylphenol react to obtain a supermolecular polymer which is used as a modifier, the supermolecular polymer comprises polymers formed by the synergistic effect or multiple effects of the intermolecular interactions, amino groups and hydroxyl groups in the supermolecular polymer react with carboxyl groups of the carboxyl nitrile rubber, the carboxyl groups are condensed with the amino groups or the hydroxyl groups to form amide bonds or ester groups, the obtained modified nitrile rubber is stressed and stretched, hydrogen bonds between hydroxyl groups and amino groups of the supermolecular polymer and hydrogen bonds between the supermolecular polymer and the carboxyl nitrile rubber are preferentially broken and dissipated in energy before the covalent bonds are broken, and the broken of the hydrogen bonds can prevent the carboxyl nitrile rubber crosslinked by the covalent bonds from being broken prematurely due to stress concentration, so that the strength and the toughness of the carboxyl nitrile rubber are remarkably improved, and the oil resistance and the wear resistance are also improved.
Claims (6)
1. An oil-resistant polyvinyl chloride cable comprises a conductor and a sheath layer, and is characterized in that the sheath layer is composed of polyvinyl chloride, modified nitrile rubber, a styrene elastomer, aniline formaldehyde resin, vinyl trimethoxy silane, an antioxidant, a vulcanizing agent, a maleic anhydride-styrene copolymer, zinc stearate, dioctyl sebacate, liquid paraffin, white carbon black and zinc oxide;
the preparation method of the modified nitrile rubber comprises the following steps:
s1, mixing 3-5 parts by weight of 2- (methacrylic acid) 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, stirring for 8-15min at 400-800rpm, adding 5-10 parts by weight of butyltriphenylphosphine bromide and 4-6 parts by weight of tosyl hydrazide, reacting for 5-8h at 40-50 ℃, and distilling under reduced pressure to remove a solvent to obtain an intermediate;
S2, mixing 4-6 parts by weight of an 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times by nitrogen, stirring for 20-40min at 200-600rpm and 40-50 ℃, adding 20-40 parts by weight of butadiene and 0.5-2 parts by weight of azodiisobutyronitrile, continuing to react for 40-80min, cooling to room temperature, removing solvent by reduced pressure distillation, washing and drying to obtain the modified nitrile rubber.
2. The oil resistant polyvinyl chloride cable of claim 1 wherein the vulcanizing agent is any one of bis-t-butylperoxyisopropyl benzene, dicumyl peroxide, t-butylphenol formaldehyde resin.
3. The oil resistant polyvinyl chloride cable of claim 1, wherein the antioxidant is any one of antioxidant 1010, antioxidant 168, antioxidant 1080, antioxidant 1076.
4. The oil resistant polyvinyl chloride cable of claim 1 wherein the conductor is any one of copper, zinc, iron.
5. The oil-resistant polyvinyl chloride cable according to claim 1, comprising a conductor and a sheath layer, wherein the sheath layer is composed of, by weight, 80 parts of polyvinyl chloride, 20 parts of modified nitrile rubber, 20 parts of a styrene-based elastomer, 10 parts of an aniline formaldehyde resin, 8 parts of vinyl trimethoxysilane, 1010 parts of an antioxidant, 2 parts of bis-tert-butyl peroxyisopropyl benzene, 10 parts of a 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;
the preparation method of the modified nitrile rubber comprises the following steps:
S1, mixing 4 parts by weight of 2- (methacrylic acid) ethyl ester 3, 5-diaminobenzoic acid, 8 parts by weight of 2-methoxy-4-vinylphenol and 80 parts by weight of N, N-dimethylformamide, stirring for 10min at 600rpm, adding 8 parts by weight of butyltriphenylphosphine bromide and 6 parts by weight of toluene sulfonyl hydrazine, reacting for 6h at 45 ℃, and distilling off the solvent under reduced pressure to obtain an intermediate;
S2, mixing 4.5 parts by weight of an 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 part by weight of ethylene diamine tetraacetic 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, vacuumizing, replacing 3 times with nitrogen, stirring for 30 minutes at 400rpm and 45 ℃, adding 30 parts by weight of butadiene and 1 part by weight of azobisisobutyronitrile, continuing to react for 50 minutes, cooling to room temperature, and obtaining modified nitrile rubber through reduced pressure distillation to remove solvent, washing and drying;
The conductor is copper.
6. The method for preparing an oil-resistant polyvinyl chloride cable according to any one of claims 1 to 5, wherein polyvinyl chloride, 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, mixed and extruded to form, and coated on the surface of a conductor to obtain the oil-resistant polyvinyl chloride cable.
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| CN104974412A (en) * | 2015-07-27 | 2015-10-14 | 上海至正道化高分子材料股份有限公司 | Vulcanized oil-resistant flame-retardant locomotive cable sheath material and preparation method thereof |
| CN115895072A (en) * | 2022-11-21 | 2023-04-04 | 青岛科技大学 | Application of supramolecular polymer in modification of carboxylated nitrile rubber, modified carboxylated nitrile rubber and preparation method thereof |
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| CN115895072A (en) * | 2022-11-21 | 2023-04-04 | 青岛科技大学 | Application of supramolecular polymer in modification of carboxylated nitrile rubber, modified carboxylated nitrile rubber and preparation method thereof |
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