CN116063806A - High-temperature wear-resistant sheath material and preparation method thereof - Google Patents
High-temperature wear-resistant sheath material and preparation method thereof Download PDFInfo
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- CN116063806A CN116063806A CN202211735792.8A CN202211735792A CN116063806A CN 116063806 A CN116063806 A CN 116063806A CN 202211735792 A CN202211735792 A CN 202211735792A CN 116063806 A CN116063806 A CN 116063806A
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 229920001230 polyarylate Polymers 0.000 claims abstract description 44
- 239000011521 glass Substances 0.000 claims abstract description 42
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims abstract description 41
- 239000011324 bead Substances 0.000 claims abstract description 36
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 24
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000000051 modifying effect Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 11
- 239000004317 sodium nitrate Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
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- 238000009413 insulation Methods 0.000 description 5
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- 230000000694 effects Effects 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
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- 239000010410 layer Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
Abstract
The invention provides a high-temperature wear-resistant sheath material which is prepared from the following raw materials in parts by weight: 100-120 parts of high-polymerization polyvinyl chloride, 0.3-0.5 part of lubricant, 0.3-0.8 part of antioxidant, 5-10 parts of heat stabilizer, 10-20 parts of ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber and 3-5 parts of modified hollow glass beads.
Description
Technical Field
The invention relates to the technical field of cables, in particular to a high-temperature wear-resistant sheath material and a preparation method thereof.
Background
With the rapid development of the communication industry, it is important to construct a safe and efficient transmission platform and system, and the wires and cables play an indispensable role in the construction of the base station. The nonmetallic outer protective layer or insulating layer of the electric wire and cable mainly has the functions of insulation, water resistance, mechanical protection and the like, and serves as a first protective layer of the electric wire and cable. The heating value of the wire and the cable in the operation process is large, so that certain heat-resistant requirements are met on the insulation and protection layer materials. In particular to a material for medium-high voltage cables, which has higher heat resistance requirement.
PVC materials are still mainstream in the wire and cable industry due to the price advantage, and in almost all occasions, some places with severe environments, especially on the construction site, the wires are often subjected to friction and impact, and the wire and cable which are not wear-resistant can have great potential safety hazards when used on the occasions, especially on high-temperature weather or equipment with high power, the surface temperature of the wires is increased, and the wear resistance and scratch resistance can be poorer. The PVC cable sheath material is poor in wear resistance, the wear resistance is poorer due to the fact that the PVC cable sheath material contains a certain amount of filling, and the sheath material is softer and softer along with the rise of temperature, so that the wear resistance is poorer, and therefore, the problem of poor wear resistance of the sheath material under the high-temperature condition is improved, and the PVC cable sheath material has important research significance.
For example, application publication No.: CN111303561a, chinese patent on publication No. 2020, 06 and 19, discloses a method for preparing a polyvinyl chloride modified sheath material and a cable, wherein the bending at-40 ℃ and flame retardance meet VW-1 requirements by adjusting the dosage of dioctyl adipate plasticizer and modifier TPEE resin, and the towline (wear resistance) is made to meet more than 4 tens of millions times by adjusting the dosages of polyester plasticizer, TPEE resin and PU resin, so that the number of times of towline is greatly increased. However, the polyvinyl chloride modified sheath material disclosed by the invention is focused on wear resistance and low-temperature bending performance, and the high-temperature resistance of the polyvinyl chloride modified sheath material is not greatly improved.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a high-temperature wear-resistant sheath material and a preparation method thereof, which are used for solving the problems of poor wear resistance and poor high-temperature resistance of the existing polyvinyl chloride cable sheath material.
To achieve the above and other related objects, the present invention is achieved by including the following technical means.
The invention provides a high-temperature wear-resistant sheath material which is prepared from the following raw materials in parts by weight: 100 to 120 parts of high polymerization degree polyvinyl chloride, 0.3 to 0.5 part of lubricant, 0.3 to 0.8 part of antioxidant, 5 to 10 parts of heat stabilizer, 10 to 20 parts of modified thermotropic liquid crystal polyarylate fiber and 3 to 5 parts of modified hollow glass microsphere.
In order to improve the heat resistance and the wear resistance of the sheath material, the high-polymerization-degree polyvinyl chloride (HPVC) with large molecular weight is particularly adopted as a matrix resin material, and compared with the common PVC, the HPVC has the advantages of large chain length and crimping property, increased entanglement points among molecular chains, high crystallinity and excellent high-temperature resistance and mechanical strength. However, the high polymerization degree polyvinyl chloride (HPVC) has strong acting force among molecular chains, difficult sliding among the molecular chains and poor plasticizing performance, so that the wear resistance cannot be improved. In the prior art, a plasticizer is generally added to reduce the melting temperature of the resin, so that the fluidity of the resin in a molten state and the softness of a product are improved, and the processability of the product is improved. However, the addition of a large amount of plasticizer can reduce the flame retardant properties of the sheathing compound, the plasticizer is easy to solidify at low temperature, migrate to the surface of the material, volatilize easily, have odor, and the finished sheathing product becomes hard at a later stage, resulting in the loss of the basic properties of the material. The present application avoids the use of traditional plasticizers, but improves processability by new ideas.
Thermotropic liquid crystal polyarylate is a thermotropic liquid crystal polymer formed by connecting aromatic rings through ester bonds, and is formed by linking rigid rod-shaped molecular units, and liquid crystals can be formed in the heating process. When the thermoplastic resin is in a liquid crystal state in the melt processing process, the thermoplastic resin can be spontaneously oriented along the flowing direction under the action of a force field due to the rigidity of the molecular structure, obvious shear thinning behavior is generated, and a reinforcing phase with an oriented structure is formed in situ in matrix resin, so that the thermoplastic resin can be reinforced and the processing fluidity can be improved. The thermotropic liquid crystal polyarylate fiber is a high-performance fiber obtained by melt spinning and heat treatment of the thermotropic liquid crystal polyarylate, not only maintains the good fluidity of the thermotropic liquid crystal polyarylate, but also has high strengthThe application overcomes the problems of difficult plasticization and poor wear resistance of high-polymerization-degree polyvinyl chloride by adding the thermotropic liquid crystal polyarylate fiber into a system, but the thermotropic liquid crystal polyarylate fiber has very smooth surface, high surface chemical inertness and no active group, so that the interface bonding property between the thermotropic liquid crystal polyarylate fiber and a high-polymerization-degree polyvinyl chloride matrix resin material is poor, the surface of the polyethylene glycol phenyl ether is modified by the ethylene glycol phenyl ether, and small molecules of the ethylene glycol phenyl ether enter the surface layer of the thermotropic liquid crystal polyarylate fiber through diffusion and are combined with molecular chains of the polyethylene glycol phenyl ether in a hydrogen bond mode, so that the surface layer of the fiber is moderately swelled, the surface roughness is improved, the interfacial adhesion of the thermotropic liquid crystal polyarylate fiber and a polyvinyl chloride matrix resin material with high polymerization degree is improved, and the dispersibility is improved, so that the plasticizing performance of the thermotropic liquid crystal polyarylate fiber is effectively improved. The thermotropic liquid crystal polyarylate fiber has obvious sheath-core structure, high fiber sheath orientation, low core orientation and larger stress effect, so that molecular chains or chain segments tend to be arranged in parallel along the same direction, aggregation is easy to occur, and the thermotropic liquid crystal polyarylate fiber has certain brittleness; according to the application, the isotropic hollow glass beads are added into the system, and the internal stress generated by the thermotropic liquid crystal polyarylate fibers is dispersed or eliminated through the hollow glass beads, so that the ordered distribution of the thermotropic liquid crystal polyarylate fibers is damaged, the degree of confusion is improved, and the dispersion performance is improved. Meanwhile, the hollow glass beads can also be used as filler to improve mechanical strength and reduce raw material cost, the hollow structure of the hollow glass beads has extremely high melting point and inertness, the wall is thin and hollow, the cavity is in semi-vacuum, and only very small amount of gas (N) 2 、H 2 CO and CO 2 Etc.), the heat conduction is very slow and very micro to form a heat insulation layer, the heat preservation and the heat insulation are excellent, and the high temperature resistance of the sheath material can be further improved. However, the hollow glass beads are inorganic materials, the surfaces of the hollow glass beads are hydrophilic and are difficult to uniformly disperse in a resin matrix, and the modified hollow glass beads are adopted to effectively improve the interfacial adhesion between the hollow glass beads and the resin matrix so as to overcome the problems. The lubricant, the antioxidant and the heat stabilizer are used as processing aids to synergistically improve the high temperature resistance and the wear resistance of the sheath material with other components.
Preferably, the polymerization degree of the polyvinyl chloride with high polymerization degree is 1700-2500, such as 1700-2000, 2000-2500.
Preferably, the modified thermotropic liquid crystal polyarylate fiber is prepared by the following method: placing the thermotropic liquid crystal polyarylate fiber into a modifying liquid, and carrying out ultrasonic treatment for 20-30 min at 125-135 ℃, wherein the modifying liquid is a mixed aqueous solution of ethylene glycol phenyl ether and sodium nitrate, the concentration of the ethylene glycol phenyl ether in the modifying liquid is 45-60 g/L, and the concentration of the sodium nitrate in the modifying liquid is 15-20 g/L; the mass volume ratio of the thermotropic liquid crystal polyarylate fiber to the modifying liquid is 10-20 g/L.
In the technical scheme, the thermotropic liquid crystal polyarylate fiber adsorbs OH generated by ionization of water in water - And take negative charge, na in the modified liquid + Can reduce Zeta potential of fiber surface, increase adsorption rate of ethylene glycol phenyl ether on fiber surface, promote diffusion into surface amorphous region, change fiber surface structure, but excessive Na + The Zeta potential is reversely increased, so that the sodium nitrate with the concentration has the best modifying effect. When the concentration of the ethylene glycol phenyl ether is too high, aggregation effect can be generated on the surface of the fiber and even the surface layer of the fiber is wrapped, so that the modification of the fiber is weakened.
Preferably, the linear density of the modified thermotropic liquid crystal polyarylate fiber is 2.5-5.0 dtex, and the breaking strength is 4.5-5.5 GPa.
Preferably, the particle size of the modified hollow glass beads is 5-20 μm, and the wall thickness is 1-3 μm.
Preferably, the modified hollow glass beads are prepared by the following method: dispersing the silane coupling agent and the hollow glass beads in ethanol, stirring at a high speed for reaction, and filtering and washing with ethanol after the reaction is finished to obtain the modified hollow glass beads. The silane coupling agent has hydrophilic functional groups and hydrophobic functional groups, wherein the hydrophilic functional groups are polar groups, so that chemical reaction can be performed on the surfaces of the hollow glass microspheres, the hydrophobic functional groups are nonpolar groups, and chemical reaction can be performed with the high-polymerization-degree polyvinyl chloride, and the interfacial adhesion between the hollow glass microspheres and the high-polymerization-degree polyvinyl chloride matrix is effectively improved.
Preferably, the reaction temperature is 25-35 ℃ and the reaction time is 16-24 h.
Preferably, the rotating speed of high-speed stirring is 15000-35000 r/min, and the stirring time is 240-320 s.
Preferably, the mass ratio of the silane coupling agent to the hollow glass beads is (2.0-2.5): 100, such as (2.0-2.25): 100, (2.25 to 2.5): 100.
preferably, the silane coupling agent is selected from one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (β -methoxyethoxy) silane.
Preferably, the lubricant is selected from one or more of paraffin wax, polyethylene wax and calcium stearate.
Preferably, the antioxidant is selected from one or a mixture of two of the antioxidants 1010 and 168.
Preferably, the heat stabilizer is a calcium zinc stabilizer.
The invention also provides a preparation method of the high-temperature wear-resistant sheath material, which comprises the steps of uniformly mixing the raw materials of the components, carrying out melt mixing extrusion in a screw extruder, and granulating to obtain the high-temperature wear-resistant sheath material.
Preferably, the screw extruder comprises 11 temperature zones, the temperature of each temperature zone being as follows: 120 ℃,120 ℃,140 ℃,150 ℃,150 ℃,170 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃; the temperature of the machine head is 160-180 ℃ and the rotating speed of the host machine is 200-300 rpm.
As described above, the present invention has the following advantageous effects:
(1) According to the high-temperature wear-resistant sheath material disclosed by the invention, all components are synergistic, plasticizing and wear resistance are improved by adding the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber, internal stress generated by the thermotropic liquid crystal polyarylate fiber is dispersed or eliminated by adopting the modified hollow glass beads, the wall is thin and hollow, the heat preservation and heat insulation are excellent, and the high-temperature resistance and the mechanical property of the sheath material can be further improved;
(2) The preparation method is simple to operate, has no special requirement on equipment, is easy to control technological parameters, and is easy to industrialize.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
It should be understood that the process equipment or devices not specifically identified in the examples below are all conventional in the art.
Furthermore, it is to be understood that the reference to one or more method steps in this disclosure does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that the combined connection between one or more devices/means mentioned in the present invention does not exclude that other devices/means may also be present before and after the combined device/means or that other devices/means may also be interposed between these two explicitly mentioned devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In the examples below of this application, thermotropic liquid crystalline polyarylate fibers were purchased from colali japan. The heat stabilizer was purchased from Taizhou incorporated calcium zinc stabilizer model FC-16A+.
Example 1
The embodiment provides a high-temperature wear-resistant sheath material which is prepared from the following raw materials: 110kg of high-polymerization polyvinyl chloride (polymerization degree 1700-2000), 0.4kg of polyethylene wax, 0.6kg of antioxidant 1010, 8kg of calcium-zinc stabilizer, 15kg of ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber (linear density 2.5-5.0 dtex, breaking strength 4.5-5.5 GPa) and 4kg of modified hollow glass beads (particle size 5-10 mu m and wall thickness 1-2 mu m).
In the embodiment, the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber is prepared by the following method: placing the thermotropic liquid crystal polyarylate fiber into a modifying liquid, and carrying out ultrasonic treatment at 130 ℃ for 25min, wherein the modifying liquid is a mixed aqueous solution of ethylene glycol phenyl ether and sodium nitrate, the concentration of the ethylene glycol phenyl ether in the modifying liquid is 50g/L, and the concentration of the sodium nitrate in the modifying liquid is 18g/L; the mass volume ratio of the thermotropic liquid crystal polyarylate fiber to the modifying liquid is 18g/L.
In this embodiment, the modified hollow glass beads are prepared by the following method: dispersing a silane coupling agent (vinyl triethoxysilane) and the hollow glass beads in ethanol, stirring at a high speed for reaction, wherein the stirring speed is 20000r/min, the stirring time is 300s, the reaction temperature is 30 ℃, the reaction time is 20h, and filtering and washing with ethanol after the reaction is completed to obtain the modified hollow glass beads. The mass ratio of the silane coupling agent to the hollow glass beads is 2.25:100.
the embodiment also provides a preparation method of the high-temperature wear-resistant sheath material, which comprises the steps of uniformly mixing the raw materials of the components, melting, mixing, extruding and granulating in a screw extruder to obtain the high-temperature wear-resistant sheath material. The screw extruder comprises 11 temperature zones, and the temperature of each temperature zone is as follows: 120 ℃,120 ℃,140 ℃,150 ℃,150 ℃,170 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃; the temperature of the machine head is 180 ℃ and the rotating speed of the host machine is 250rpm.
Example 2
The embodiment provides a high-temperature wear-resistant sheath material which is prepared from the following raw materials: 120kg of high-polymerization polyvinyl chloride (the polymerization degree is 2000-2500), 0.5kg of calcium stearate, 168.8 kg of antioxidant, 10kg of calcium-zinc stabilizer, 20kg of ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber (the linear density is 2.5-5.0 dtex, the breaking strength is 4.5-5.5 GPa) and 5kg of modified hollow glass beads (the particle size is 5-20 mu m and the wall thickness is 1-3 mu m).
In the embodiment, the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber is prepared by the following method: placing the thermotropic liquid crystal polyarylate fiber into a modifying liquid, and carrying out ultrasonic treatment for 30min at 125 ℃, wherein the modifying liquid is a mixed aqueous solution of ethylene glycol phenyl ether and sodium nitrate, the concentration of the ethylene glycol phenyl ether in the modifying liquid is 60g/L, and the concentration of the sodium nitrate in the modifying liquid is 20g/L; the mass volume ratio of the thermotropic liquid crystal polyarylate fiber to the modifying liquid is 20g/L.
In this embodiment, the modified hollow glass beads are prepared by the following method: dispersing a silane coupling agent (vinyl triethoxysilane) and the hollow glass beads in ethanol, stirring at a high speed for reaction, wherein the stirring speed is 15000r/min, the stirring time is 320s, the reaction temperature is 25 ℃, the reaction time is 24h, and filtering and washing with ethanol after the reaction is completed to obtain the modified hollow glass beads. The mass ratio of the silane coupling agent to the hollow glass beads is 2.0:100.
the embodiment also provides a preparation method of the high-temperature wear-resistant sheath material, which comprises the steps of uniformly mixing the raw materials of the components, melting, mixing, extruding and granulating in a screw extruder to obtain the high-temperature wear-resistant sheath material. The screw extruder comprises 11 temperature zones, and the temperature of each temperature zone is as follows: 120 ℃,120 ℃,140 ℃,150 ℃,150 ℃,170 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃; the temperature of the machine head is 180 ℃ and the rotating speed of the host machine is 200rpm.
Example 3
The embodiment provides a high-temperature wear-resistant sheath material which is prepared from the following raw materials: 100kg of high polymerization degree polyvinyl chloride (polymerization degree is 1700-2500), 0.3kg of paraffin wax, 168.3 kg of antioxidant, 5kg of calcium zinc stabilizer, 10kg of ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber (linear density is 2.5-5.0 dtex, breaking strength is 4.5-5.5 GPa) and 3kg of modified hollow glass microsphere (particle size is 5-20 mu m, wall thickness is 1-3 mu m).
In the embodiment, the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber is prepared by the following method: placing the thermotropic liquid crystal polyarylate fiber into a modified liquid, and carrying out ultrasonic treatment for 20min at 135 ℃, wherein the modified liquid is a mixed aqueous solution of ethylene glycol phenyl ether and sodium nitrate, the concentration of the ethylene glycol phenyl ether in the modified liquid is 45g/L, and the concentration of the sodium nitrate in the modified liquid is 15g/L; the mass volume ratio of the thermotropic liquid crystal polyarylate fiber to the modifying liquid is 10g/L.
In this embodiment, the modified hollow glass beads are prepared by the following method: dispersing a silane coupling agent (vinyl triethoxysilane) and the hollow glass beads in ethanol, stirring at a high speed for reaction, wherein the stirring speed is 35000r/min, the stirring time is 240s, the reaction temperature is 35 ℃, the reaction time is 16h, and filtering and washing with ethanol after the reaction is completed to obtain the modified hollow glass beads. The mass ratio of the silane coupling agent to the hollow glass beads is 2.5:100.
the embodiment also provides a preparation method of the high-temperature wear-resistant sheath material, which comprises the steps of uniformly mixing the raw materials of the components, melting, mixing, extruding and granulating in a screw extruder to obtain the high-temperature wear-resistant sheath material. The screw extruder comprises 11 temperature zones, and the temperature of each temperature zone is as follows: 120 ℃,120 ℃,140 ℃,150 ℃,150 ℃,170 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃; the temperature of the machine head is 180 ℃ and the rotating speed of the host machine is 300rpm.
Comparative example 1
Comparative example 1 differs from example 1 in that no modified hollow glass microspheres were added and the rest of the process was exactly the same.
Comparative example 2
Comparative example 2 differs from example 1 in that the thermotropic liquid crystalline polyarylate fiber was not modified, and the rest of the process was exactly the same.
The performances of the high-temperature wear-resistant sheath materials prepared in examples 1-3 and comparative examples 1 and 2 were tested, and the test methods and results are shown in Table 1:
abrasion resistance test: on an Amsler abrasion tester, each group of materials is detected, and the detection coefficients are as follows: grinding disc:
rotational speed: 185r/min, hardness: 58-60 HRC, surface roughness: ra=0.4 μm, time to finish: 2h, load: 30kg, the abrasion rate (%).
TABLE 1 test criteria and test results
The above examples are provided to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, many modifications and variations of the methods and compositions of the invention set forth herein will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the present invention.
Claims (10)
1. The high-temperature wear-resistant sheath material is characterized by being prepared from the following raw materials in parts by weight: 100-120 parts of high-polymerization-degree polyvinyl chloride, 0.3-0.5 part of lubricant, 0.3-0.8 part of antioxidant, 5-10 parts of heat stabilizer, 10-20 parts of ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber and 3-5 parts of modified hollow glass microspheres.
2. The high temperature wear resistant sheath material according to claim 1, wherein: the polymerization degree of the polyvinyl chloride with high polymerization degree is 1700-2500.
3. The high temperature wear resistant sheath material according to claim 1, wherein: the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber is prepared by the following method: placing the thermotropic liquid crystal polyarylate fiber in a modified liquid, and carrying out ultrasonic treatment for 20-30 min at 125-135 ℃, wherein the modified liquid is a mixed aqueous solution of ethylene glycol phenyl ether and sodium nitrate, the concentration of the ethylene glycol phenyl ether in the modified liquid is 45-60 g/L, and the concentration of the sodium nitrate in the modified liquid is 15-20 g/L; the mass volume ratio of the thermotropic liquid crystal polyarylate fiber to the modifying liquid is 10-20 g/L.
4. A high temperature wear resistant sheath material according to claim 3, wherein: the linear density of the ethylene glycol phenyl ether modified thermotropic liquid crystal polyarylate fiber is 2.5-5.0 dtex, and the breaking strength is 4.5-5.5 GPa.
5. The high temperature wear resistant sheath material according to claim 1, wherein: the particle size of the modified hollow glass beads is 5-20 mu m, and the wall thickness is 1-3 mu m.
6. The high temperature wear resistant sheath material according to claim 1, wherein: the modified hollow glass beads are prepared by the following method: dispersing the silane coupling agent and the hollow glass beads in ethanol, stirring at a high speed for reaction, and filtering and washing with ethanol after the reaction is finished to obtain the modified hollow glass beads.
7. The high temperature wear resistant sheath material according to claim 6, wherein: the mass ratio of the silane coupling agent to the hollow glass beads is (2.0-2.5): 100.
8. the high temperature wear resistant sheath material according to claim 1, wherein: the lubricant is selected from one or more of paraffin wax, polyethylene wax and calcium stearate; the antioxidant is selected from one or two of antioxidant 1010 and antioxidant 168; the heat stabilizer is a calcium-zinc stabilizer.
9. A method for preparing the high-temperature wear-resistant sheath material according to any one of claims 1 to 8, which is characterized in that: and after uniformly mixing the raw materials of the components, melting, mixing, extruding and granulating in a screw extruder to obtain the high-temperature wear-resistant sheath material.
10. The method of manufacturing according to claim 9, wherein: the screw extruder comprises 11 temperature zones, and the temperature of each temperature zone is as follows: 120 ℃,120 ℃,140 ℃,150 ℃,150 ℃,170 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃; the temperature of the machine head is 160-180 ℃, and the rotating speed of the host machine is 200-300 rpm.
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