CN115403877A - Insulating polyvinyl chloride cable composite material - Google Patents
Insulating polyvinyl chloride cable composite material Download PDFInfo
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- CN115403877A CN115403877A CN202210549123.5A CN202210549123A CN115403877A CN 115403877 A CN115403877 A CN 115403877A CN 202210549123 A CN202210549123 A CN 202210549123A CN 115403877 A CN115403877 A CN 115403877A
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- polyvinyl chloride
- boron nitride
- composite material
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- chloride cable
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 56
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 229910052582 BN Inorganic materials 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical class [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 21
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- 229940043237 diethanolamine Drugs 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- SJUMVKPSWOVVBX-UHFFFAOYSA-N 4-(bromomethyl)benzenethiol Chemical compound SC1=CC=C(CBr)C=C1 SJUMVKPSWOVVBX-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- -1 diethanol amino thiophenol Chemical compound 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000010382 chemical cross-linking Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 15
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 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 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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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
- 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
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- Polymers & Plastics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyvinyl chloride and discloses an insulating polyvinyl chloride cable composite material.A diethanolaminephenylphenol reacts with isocyanated boron nitride, then the diethanolaminephenylphenol reacts with diisocyanate monomers to generate hyperbranched polymerization reaction, and then the reaction product is alkalized by sodium hydroxide to generate sodium mercaptan salt, so that sodium mercaptan salt hyperbranched polyurethane modified boron nitride is obtained, polyvinyl chloride is modified, and nano boron nitride can be well dispersed in a polyvinyl chloride matrix; meanwhile, in the plasticizing and crosslinking process, the surface active sodium mercaptan salt and chlorine atoms of the polyvinyl chloride are subjected to substitution reaction, so that hyperbranched polyurethane modified boron nitride and the polyvinyl chloride are subjected to chemical crosslinking, the interface binding force of the nano boron nitride and the polyvinyl chloride cable material is enhanced, the thermal decomposition temperature of the polyvinyl chloride cable material is increased, and higher thermal stability and insulativity are represented.
Description
Technical Field
The invention relates to the technical field of polyvinyl chloride, in particular to an insulating polyvinyl chloride cable composite material.
Background
The polyvinyl chloride is widely applied to the wire and cable industry and mainly used as an insulating layer and a protective layer, so that the improvement of the insulativity and the thermal stability of the polyvinyl chloride has main significance, and nano materials such as graphite are utilizedPolyvinyl chloride is modified by alkene, nano titanium dioxide and the like, so that the heat resistance, the heat conductivity, the mechanical strength and other properties of the material can be effectively improved, such as PVC/GR/SiO 2 Preparation of cable jackets and flame retardant property research, reports that the mechanical strength and flame retardant property of cable materials of polyvinyl chloride are improved by compounding graphene, nano particle silicon dioxide and polyvinyl chloride.
The nanometer boron nitride has very high resistivity and heat conductivity coefficient, can effectively improve the comprehensive properties of materials such as insulation and heat conduction, for example, the preparation of low-shrinkage heat-resistant oil-resistant polyvinyl chloride/boron nitride composite materials and the performance research thereof, report that the combination of polyvinyl chloride and boron nitride can be more compact by adopting silane coupling agent to carry out surface treatment on boron nitride particles, and the thermal property and the oil resistance of the composite materials are improved.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an insulating polyvinyl chloride cable composite material, which solves the problem that a polyvinyl chloride cable material is poor in insulating property and heat resistance.
(II) technical scheme
In order to realize the purpose, the invention provides the following technical scheme: an insulating polyvinyl chloride cable composite material is prepared by the following steps:
(1) Dissolving diethanol amine, 4-bromomethyl thiophenol and potassium carbonate into a reaction solvent, stirring and reacting at 45-70 ℃ for 12-24h, carrying out reduced pressure distillation after reaction, washing, adding ethyl acetate and distilled water into a product, and carrying out extraction separation to obtain diethanol amino thiophenol.
(2) Adding nano boron nitride into a sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into N, N-dimethylformamide, adding diisocyanate and dibutyltin dilaurate, and heating for reaction to obtain the isocyanated boron nitride.
(3) Ultrasonically dispersing isocyanated boron nitride into N, N-dimethylformamide, adding diethanolaminephenylphenol, dropwise adding dibutyltin dilaurate in nitrogen atmosphere, heating to 70-90 ℃, stirring for reaction for 1-2h, then adding diisocyanate, stirring for reaction for 5-15h, filtering a solvent after reaction, washing, adding a product into a sodium hydroxide solution, stirring for 1-3h at 40-60 ℃, centrifugally separating after reaction, and washing with distilled water to obtain the mercaptan sodium salt hyperbranched polyurethane modified boron nitride.
(4) Adding polyvinyl chloride, mercapto hyperbranched polyurethane modified boron nitride, a lubricant, a stabilizer and a plasticizer into a plasticator, plasticizing and crosslinking for 15-25min at 170-185 ℃, and then placing the materials into a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
Preferably, the reaction mass ratio of the diethanol amine, the 4-bromomethylthiophenol and the potassium carbonate in the step (1) is 100-180.
Preferably, the reaction solvent in (1) is acetone, tetrahydrofuran, acetonitrile or 1, 4-dioxane.
Preferably, the weight ratio of the isocyanated boron nitride, the diethanolaminephenylphenol, the dibutyltin dilaurate and the diisocyanate in the step (3) is (100).
Preferably, the mass fraction of the sodium hydroxide solution in the step (3) is 2-8%.
Preferably, the amount of the mercapto hyperbranched polyurethane modified boron nitride in (4) is 3-15%.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the insulating polyvinyl chloride cable composite material, diethanol amine thiophenol monomer is obtained by reacting diethanol amine with 4-bromomethyl thiophenol, and then reacts with isocyanate group on the surface of isocyanated boron nitride, so that hydroxyl and sulfydryl are introduced into the surface of the boron nitride, the sulfydryl and the hydroxyl are used as polymerization sites, the diethanol amine thiophenol and diisocyanate monomer are subjected to hyperbranched polymerization reaction by an in-situ polymerization method, the reaction ratio of the diethanol amine thiophenol is controlled, the sulfydryl-containing hyperbranched polyurethane modified boron nitride is obtained, the sulfydryl is alkalized by sodium hydroxide to generate sodium mercaptan salt, the sodium mercaptan hyperbranched polyurethane modified boron nitride is obtained, and the organic modification of the surface of the nano boron nitride is realized.
The sodium mercaptan hyperbranched polyurethane modified boron nitride is used as a functional modifier to modify polyvinyl chloride, and after the nano boron nitride is organically modified, the nano boron nitride has better compatibility with polyvinyl chloride and can be well dispersed in a polyvinyl chloride matrix; meanwhile, in the plasticizing and crosslinking process, the surface active thiol sodium salt of the nano boron nitride and chlorine atoms of polyvinyl chloride are subjected to substitution reaction, so that hyperbranched polyurethane modified boron nitride and polyvinyl chloride are subjected to chemical crosslinking, the interface bonding force of the nano boron nitride and the polyvinyl chloride cable material is enhanced, the hyperbranched polyurethane modified boron nitride can better enhance and modify the polyvinyl chloride cable material, a stable chemical crosslinking network is formed between the hyperbranched polyurethane modified boron nitride and the polyvinyl chloride cable material, the thermal decomposition temperature of the polyvinyl chloride cable material is obviously improved, higher thermal stability is shown, meanwhile, boron nitride nanoparticles are uniformly dispersed in a polyvinyl chloride matrix, a continuous and stable insulating and heat conducting network is formed, and the polyethylene insulating property and the heat conducting heat resistance of the cable material are effectively improved.
Drawings
FIG. 1 is a reaction scheme for preparing diethanolaminesulfentol.
FIG. 2 is a reaction diagram for preparing sodium mercaptan salt hyperbranched polyurethane modified boron nitride.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: an insulating polyvinyl chloride cable composite material is prepared by the following steps:
(1) Dissolving diethanol amine, 4-bromomethyl thiophenol and potassium carbonate with the reaction mass ratio of 100-260.
(2) Adding nano boron nitride into a sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into N, N-dimethylformamide, adding diisocyanate and dibutyltin dilaurate, and heating for reaction to obtain isocyanated boron nitride.
(3) Ultrasonically dispersing isocyanated boron nitride into N, N-dimethylformamide, adding diethanolaminephenylphenol, dropwise adding dibutyltin dilaurate in nitrogen atmosphere, heating to 70-90 ℃, stirring for reaction for 1-2h, then adding diisocyanate, controlling the weight ratio of isocyanated boron nitride to diethanolaminephenylphenol to dibutyltin dilaurate to be 100.
(4) Adding polyvinyl chloride, 3-15% of mercapto hyperbranched polyurethane modified boron nitride, a lubricant, a stabilizer and a plasticizer into a plasticator, plasticizing and crosslinking for 15-25min at 170-185 ℃, and then placing the materials into a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
Example 1
(1) Dissolving 0.1g of diethanol amine, 0.18g of 4-bromomethylthiophenol and 0.11g of potassium carbonate in 5mL of acetone, stirring and reacting at 70 ℃ for 18h, carrying out reduced pressure distillation after reaction, washing, adding ethyl acetate and distilled water into the product, and carrying out extraction separation to obtain diethanolammonium thiophenol.
(2) Adding 0.5g of nano boron nitride into a 20% sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into 100mL of N, N-dimethylformamide, adding 2g of toluene diisocyanate and 0.02g of dibutyltin dilaurate, and heating for reaction to obtain the isocyanated boron nitride.
(3) Ultrasonically dispersing 0.1g of isocyanated boron nitride into 50mL of N, N-dimethylformamide, adding 0.3g of diethanolaminephenylthiol, dropwise adding 0.005g of dibutyltin dilaurate in a nitrogen atmosphere, heating to 90 ℃, stirring for reaction for 1h, then adding 0.24g of toluene diisocyanate, stirring for reaction for 12h, filtering a solvent after reaction, adding a product into a 5% sodium hydroxide solution after washing, stirring for 3h at 40 ℃, performing centrifugal separation after reaction, and washing with distilled water to obtain the thiol sodium salt hyperbranched polyurethane modified boron nitride.
(4) Adding polyvinyl chloride, 3% of mercapto hyperbranched polyurethane modified boron nitride, 4% of calcium stearate, 3% of calcium zinc stabilizer and 45% of dioctyl phthalate into a plasticator, plasticizing and crosslinking for 15min at 180 ℃, and then placing the materials into a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
Example 2
(1) Dissolving 0.1g of diethanol amine, 0.23g of 4-bromomethylthiophenol and 0.14g of potassium carbonate in 10mL of tetrahydrofuran, stirring and reacting at 45 ℃ for 24 hours, carrying out reduced pressure distillation after reaction, washing, adding ethyl acetate and distilled water into a product, and carrying out extraction separation to obtain diethanolammonium thiophenol.
(2) Adding 0.5g of nano boron nitride into 25% sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into 200mL of N, N-dimethylformamide, adding 3.2 g of toluene diisocyanate and 0.03g of dibutyltin dilaurate, and heating for reaction to obtain the isocyanated boron nitride.
(3) Ultrasonically dispersing 0.1g of isocyanated boron nitride into 40mL of N, N-dimethylformamide, adding 0.6g of diethanolaminephenylphenol, dropwise adding 0.012g of dibutyltin dilaurate in the nitrogen atmosphere, heating to 70 ℃, stirring for reaction for 2 hours, then adding 0.45g of toluene diisocyanate, stirring for reaction for 5 hours, filtering a solvent after the reaction, adding a product into 8% sodium hydroxide solution after washing, stirring for 3 hours at 60 ℃, performing centrifugal separation after the reaction, and washing with distilled water to obtain the thiol sodium salt hyperbranched polyurethane modified boron nitride.
(4) Adding polyvinyl chloride, 8% of mercapto hyperbranched polyurethane modified boron nitride, 3% of calcium stearate, 3% of calcium zinc stabilizer and 40% of dioctyl phthalate into a plasticator, plasticizing and crosslinking for 25min at 170 ℃, and then placing the materials in a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
Example 3
(1) Dissolving 0.1g of diethanol amine, 0.26g of 4-bromomethylthiophenol and 0.16g of potassium carbonate into 10mL of 1, 4-dioxane, stirring and reacting at 60 ℃ for 18 hours, distilling under reduced pressure after reaction, washing, adding ethyl acetate and distilled water into a product, and performing extraction separation to obtain diethanolaminephenylthiophenol.
(2) Adding 0.5g of nano boron nitride into a 20% sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into 200mL of N, N-dimethylformamide, adding 4g of isophorone diisocyanate and 0.04g of dibutyltin dilaurate, and heating for reaction to obtain the isocyanated boron nitride.
(3) Ultrasonically dispersing 0.1g of isocyanated boron nitride into 50mL of N, N-dimethylformamide, adding 0.8g of diethanolaminothiophenol, dropwise adding 0.015g of dibutyltin dilaurate in nitrogen atmosphere, heating to 70 ℃, stirring for reaction for 2 hours, then adding 0.6g of isophorone diisocyanate, stirring for reaction for 15 hours, filtering a solvent after reaction, adding a product into a 5% sodium hydroxide solution after washing, stirring for 2 hours at 50 ℃, performing centrifugal separation after reaction, and washing with distilled water to obtain the sodium mercaptan hyperbranched polyurethane modified boron nitride.
(4) Adding polyvinyl chloride, 15% of mercapto hyperbranched polyurethane modified boron nitride, 3% of calcium stearate, 3% of calcium zinc stabilizer and 50% of dioctyl phthalate into a plasticator, plasticizing and crosslinking for 25min at 175 ℃, and then placing the materials in a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
Comparative example 1
(1) Adding 0.5g of nano boron nitride into a 20% sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into 100mL of N, N-dimethylformamide, adding 2.8 g of isophorone diisocyanate and 0.03g of dibutyltin dilaurate, and heating for reaction to obtain the isocyanated boron nitride.
(2) Adding polyvinyl chloride, 3% of mercapto hyperbranched polyurethane modified boron nitride, 2% of calcium stearate, 3% of calcium zinc stabilizer and 45% of dioctyl phthalate into a plasticator, plasticizing at 180 ℃ for 20 min, and then placing the materials in a flat vulcanizing machine for hot press molding to obtain the polyvinyl chloride cable composite material.
Testing the volume resistivity of the insulating polyvinyl chloride cable composite material by using an HT type digital megohmmeter, wherein the diameter of a sample specification is 10cm, the thickness is 5mm, and the volume resistivity rho = (R multiplied by A)/h; r is the insulation resistance value, A is the electrode area, and h is the sample thickness.
The thermal performance of the insulating polyvinyl chloride cable composite material is tested by adopting a TGA thermogravimetric analyzer, the heating rate is 10 ℃/min in a nitrogen atmosphere, and the temperature range is 30-800 DEG C
The foregoing embodiments are provided merely as an aid to understanding the method and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. An insulating polyvinyl chloride cable composite material is characterized in that: the preparation method of the composite material comprises the following steps:
(1) Dissolving diethanol amine, 4-bromomethylthiophenol and potassium carbonate into a reaction solvent, stirring and reacting at 45-70 ℃ for 12-24 hours, distilling under reduced pressure after reaction, washing, adding a product into ethyl acetate and distilled water, and performing extraction separation to obtain diethanol amino thiophenol;
(2) Adding nano boron nitride into a sodium hydroxide solution for activation to obtain hydroxylated nano boron nitride, then ultrasonically dispersing the hydroxylated nano boron nitride into N, N-dimethylformamide, adding diisocyanate and dibutyltin dilaurate, and heating for reaction to obtain isocyanated boron nitride;
(3) Ultrasonically dispersing isocyanated boron nitride into N, N-dimethylformamide, adding diethanolaminodithiophene, dropwise adding dibutyltin dilaurate in nitrogen atmosphere, heating to 70-90 ℃, stirring for reacting for 1-2h, then adding diisocyanate, stirring for reacting for 5-15h, filtering a solvent after reacting, washing, adding a product into a sodium hydroxide solution, stirring for 1-3h at 40-60 ℃, centrifugally separating after reacting, and washing with distilled water to obtain the sodium mercaptan hyperbranched polyurethane modified boron nitride;
(4) Adding polyvinyl chloride, sulfydryl hyperbranched polyurethane modified boron nitride, a lubricant, a stabilizer and a plasticizer into a plasticator, plasticizing and crosslinking for 15-25min at 170-185 ℃, and then placing the materials into a flat vulcanizing machine for hot press molding to obtain the insulating polyvinyl chloride cable composite material.
2. The insulating polyvinyl chloride cable composite material of claim 1, wherein: the reaction mass ratio of diethanol amine, 4-bromomethylthiophenol and potassium carbonate in the step (1) is (100).
3. The insulating polyvinyl chloride cable composite material of claim 1, wherein: the reaction solvent in the step (1) is acetone, tetrahydrofuran, acetonitrile or 1, 4-dioxane.
4. The insulating polyvinyl chloride cable composite material of claim 1, wherein: the weight ratio of the isocyanated boron nitride, the diethanolaminodenethiophenol, the dibutyltin dilaurate and the diisocyanate in the step (3) is (100).
5. The insulating polyvinyl chloride cable composite material of claim 1, wherein: the mass fraction of the sodium hydroxide solution in the step (3) is 2-8%.
6. The insulating polyvinyl chloride cable composite material of claim 1, wherein: the using amount of the mercapto hyperbranched polyurethane modified boron nitride in the step (4) is 3-15%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678148A (en) * | 2022-12-06 | 2023-02-03 | 深圳新联胜光电科技有限公司 | Polyethylene sheath material for optical fiber cable and preparation method thereof |
| CN115928250A (en) * | 2022-12-12 | 2023-04-07 | 南京众山电池电子有限公司 | Preparation method and application of polyester fiber insulating material |
| CN117133506A (en) * | 2023-10-17 | 2023-11-28 | 安徽鑫海高导新材料有限公司 | Temperature-resistant copper conductor cable for computer and preparation method thereof |
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2022
- 2022-05-20 CN CN202210549123.5A patent/CN115403877A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678148A (en) * | 2022-12-06 | 2023-02-03 | 深圳新联胜光电科技有限公司 | Polyethylene sheath material for optical fiber cable and preparation method thereof |
| CN115678148B (en) * | 2022-12-06 | 2023-09-22 | 深圳新联胜光电科技有限公司 | Polyethylene sheath material for optical fiber cable and preparation method thereof |
| CN115928250A (en) * | 2022-12-12 | 2023-04-07 | 南京众山电池电子有限公司 | Preparation method and application of polyester fiber insulating material |
| CN115928250B (en) * | 2022-12-12 | 2024-05-28 | 南京众山电池电子有限公司 | Preparation method and application of polyester fiber insulating material |
| CN117133506A (en) * | 2023-10-17 | 2023-11-28 | 安徽鑫海高导新材料有限公司 | Temperature-resistant copper conductor cable for computer and preparation method thereof |
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