CN116875041A - Polyurethane composite material and preparation method and application thereof - Google Patents
Polyurethane composite material and preparation method and application thereof Download PDFInfo
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- CN116875041A CN116875041A CN202311074745.8A CN202311074745A CN116875041A CN 116875041 A CN116875041 A CN 116875041A CN 202311074745 A CN202311074745 A CN 202311074745A CN 116875041 A CN116875041 A CN 116875041A
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- composite material
- polyurethane composite
- titanium dioxide
- nano titanium
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- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 41
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 11
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002245 particle Substances 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004636 vulcanized rubber Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920005560 fluorosilicone rubber Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- -1 propylene-ethylene Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 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
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-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
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyurethane composite material, a preparation method and application thereof, wherein polymer molecular chains are introduced to the surface of nano titanium dioxide by modifying the nano titanium dioxide, so that the defect that agglomeration is easy to occur among nano titanium dioxide particles is overcome, the mechanical property of the polyurethane composite material is effectively improved, and the defect that the traditional polyurethane composite material is easy to corrode is overcome; in addition, the nano titanium dioxide particles are uniformly dispersed in the polyurethane composite material, and the titanium dioxide particles have excellent ultraviolet shielding performance, so that the damage of ultraviolet rays to the polyurethane composite material is prevented; by carrying out surface modification on the basalt fiber, the surface activity of the basalt fiber is improved, the problem of mechanical property reduction caused by basalt fiber aggregation is reduced, and the mechanical property of the polyurethane composite material is further improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyurethane composite material and a preparation method and application thereof.
Background
The submarine cable is used as a tie for offshore wind power delivery, offshore platform, island and land large power grid connection, plays an important role in the fields of offshore clean energy development, power grid internationalization, regional power grid interconnection and the like, and the safety and stability of the submarine cable are critical to the normal operation of a power system. Because the marine environment is complex, the submarine cable oscillates under the periodic action of ocean currents on the seabed, so that the submarine cable is worn, fatigued and the like, the submarine cable is mechanically damaged, the structure is damaged, and great risks are brought to the safe operation of the submarine cable; meanwhile, the marine corrosion environment can cause the degradation of the mechanical property of the submarine cable sheath, and brings great threat to the long-term safe operation of the submarine cable.
In the cabling process, a cable is protected by a cable protection tube made of polyvinyl chloride materials, the cable protection tube made of the existing polyvinyl chloride materials is general in mechanical property, poor in cable protection effect under the action of impact force, poor in wear resistance and easy to damage in a complex marine environment.
The Chinese patent document CN111363271A discloses a corrosion-resistant MPP power cable protection tube material and a preparation method thereof, wherein the power cable protection tube material comprises, by weight, 30-40 parts of polyvinyl chloride resin, 10-20 parts of propylene-ethylene random copolymer, 8-20 parts of fluorosilicone rubber, 10-20 parts of oxidized polyethylene wax, 5-15 parts of nano silica micropowder, 3-9 parts of nano calcium carbonate, 4-10 parts of white carbon black, 7-14 parts of tris (2, 4-di-tert-butylphenyl) phosphorous acid, 8-20 parts of silicon nitride, 8-18 parts of silicon carbide composite, 2-6 parts of mica powder, 4-10 parts of carbon fiber, 6-16 parts of expandable graphite, 2-4 parts of CPE flame retardant and 5-10 parts of lithium porcelain powder.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyurethane composite material, a preparation method and application thereof, and the prepared polyurethane composite material has good mechanical property and ageing resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing nano titanium dioxide in ethanol water solution, adding vinyl trimethoxy silane into the solution, stirring the solution for reaction, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding double bond-containing nano titanium dioxide and 3-butene-1-ol into deionized water, uniformly mixing, adding an initiator benzoyl peroxide into the mixture, heating and stirring for reaction, and filtering, washing and drying after the reaction is completed to obtain modified nano titanium dioxide;
(3) Uniformly stirring polyether polyol, modified nano titanium dioxide, diisocyanate and stannous octoate after vacuum dehydration, heating to 90-110 ℃ for reaction for 2-4 hours, then adding chain extender dimethylolpropionic acid, reacting for 3-5 hours at 100-120 ℃, then cooling to 30-40 ℃, adding modified basalt fiber, triethylamine and acetone, stirring for reaction for 3-4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demoulding to obtain the polyurethane composite material.
Preferably, in the step (1), the mass ratio of the nano titanium dioxide to the vinyl trimethoxysilane is 5-8:1-2.
Preferably, in the step (1), the stirring reaction temperature is 40-60 ℃, and the stirring reaction time is 2-3h.
Preferably, in the step (2), the mass ratio of the nano titanium dioxide containing double bonds, 3-butene-1-ol and benzoyl peroxide is 4-8:4-6:0.6-0.8.
Preferably, in the step (2), the reaction temperature is 60-80 ℃ and the reaction time is 2-4h.
Preferably, in the step (3), the mass ratio of the polyether polyol to the modified nano titanium dioxide to the diisocyanate to the stannous octoate to the dimethylolpropionic acid to the modified basalt fiber to the triethylamine to the acetone is 10-15:15-25:10-20:0.5-1:10-20:5-10:6-10:80-120, wherein the polyether polyol is one or more of polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolymer glycol, and the diisocyanate is one or more of hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
Preferably, in the step (3), the preparation method of the modified basalt fiber comprises the following steps: dispersing basalt fiber in ethanol water solution, adding silane coupling agent KH550, stirring at 60-70 ℃ for reaction for 1-2h, filtering, washing and drying to obtain modified basalt fiber.
Preferably, the mass ratio of the basalt fiber to the silane coupling agent KH550 is 5-10:1-2.
The invention provides the polyurethane composite material prepared by the preparation method.
The invention also provides application of the polyurethane composite material in a cable protective sleeve.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the nano titanium dioxide is modified, and the polymer molecular chain is introduced into the surface of the nano titanium dioxide, so that the defect that agglomeration is easy to occur among nano titanium dioxide particles is overcome, and meanwhile, the polymer molecular chain contains a large number of active groups, so that the titanium dioxide particles are combined into the polyurethane composite material through chemical bonds, and the mechanical property of the polyurethane composite material can be effectively improved; in addition, the nano titanium dioxide particles are uniformly dispersed in the polyurethane composite material, and the titanium dioxide particles have excellent ultraviolet shielding performance, so that the damage of ultraviolet rays to the polyurethane composite material is prevented, and the ultraviolet aging resistance of the composite material is improved.
(2) According to the invention, the surface activity of the basalt fiber is improved by carrying out surface modification on the basalt fiber, the basalt fiber is filled in the polyurethane composite material through chemical bonds, the basalt fiber and the polyurethane composite material are hardly separated, the combination is tighter, the problem of mechanical property reduction caused by basalt fiber aggregation is solved, and the mechanical property of the polyurethane composite material is further improved.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
The nano titanium dioxide used in the present invention is purchased from bisli new materials (su state) limited, mesh: 12000 mesh;
the length of basalt fiber is 0.5-1mm.
Example 1
A preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing 5g of nano titanium dioxide in 150g of 80wt% ethanol water solution, adding 1g of vinyl trimethoxy silane into the solution, stirring the solution at 40 ℃ for reaction for 3 hours, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding 4g of nano titanium dioxide containing double bonds and 4g of 3-buten-1-ol into 150g of deionized water, uniformly mixing, then adding 0.6g of initiator benzoyl peroxide into the mixture, heating and stirring the mixture at 60 ℃ for reaction for 4 hours, and after the reaction is completed, filtering, washing and drying the mixture to obtain modified nano titanium dioxide;
(3) Uniformly stirring 10g of polyoxypropylene glycol, 15g of modified nano titanium dioxide, 20g of isophorone diisocyanate and 0.5g of stannous octoate after vacuum dehydration, heating to 90 ℃ for reaction for 4 hours, then adding 10g of chain extender dimethylolpropionic acid, reacting at 100 ℃ for 5 hours, then cooling to 30 ℃, adding 5g of modified basalt fiber, 6g of triethylamine and 80g of acetone, stirring and reacting for 3 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demolding to obtain a polyurethane composite material;
the preparation method of the modified basalt fiber comprises the following steps: dispersing 5g basalt fiber in 150g of 60wt% ethanol water solution, adding 1g of silane coupling agent KH550, stirring at 60 ℃ for reaction for 2h, filtering, washing and drying to obtain modified basalt fiber.
Example 2
A preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing 8g of nano titanium dioxide in 150g of 80wt% ethanol water solution, adding 2g of vinyl trimethoxy silane into the solution, stirring the solution at 60 ℃ for reaction for 2 hours, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding 8g of nano titanium dioxide containing double bonds and 6g of 3-buten-1-ol into 150g of deionized water, uniformly mixing, then adding 0.8g of initiator benzoyl peroxide into the mixture, heating and stirring the mixture at 80 ℃ for reaction for 2 hours, and after the reaction is completed, filtering, washing and drying the mixture to obtain modified nano titanium dioxide;
(3) Uniformly stirring 15g of polytetrahydrofuran glycol, 20g of modified nano titanium dioxide, 20g of hexamethylene diisocyanate and 1g of stannous octoate after vacuum dehydration, heating to 110 ℃ for reaction for 3 hours, then adding 10g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 10g of modified basalt fiber, 8g of triethylamine and 100g of acetone, stirring and reacting for 4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demolding to obtain a polyurethane composite material;
the preparation method of the modified basalt fiber comprises the following steps: 10g basalt fiber is dispersed in 150g of 60wt% ethanol water solution, then 2g of silane coupling agent KH550 is added into the solution, the solution is stirred and reacted for 2 hours at 70 ℃, and the modified basalt fiber is obtained after filtration, washing and drying.
Example 3
A preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing 6g of nano titanium dioxide in 150g of 80wt% ethanol water solution, adding 2g of vinyl trimethoxy silane into the solution, stirring the solution at 50 ℃ for reaction for 3 hours, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding 6g of nano titanium dioxide containing double bonds and 5g of 3-buten-1-ol into 150g of deionized water, uniformly mixing, then adding 0.8g of initiator benzoyl peroxide into the mixture, heating and stirring the mixture at 80 ℃ for reaction for 3 hours, and filtering, washing and drying the mixture after the reaction is completed to obtain modified nano titanium dioxide;
(3) Stirring 12g of tetrahydrofuran-propylene oxide copolymer glycol, 25g of modified nano titanium dioxide, 20g of dicyclohexylmethane diisocyanate and 0.8g of stannous octoate uniformly after vacuum dehydration, heating to 100 ℃ for reaction for 4 hours, then adding 20g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 8g of modified basalt fiber, 10g of triethylamine and 120g of acetone, stirring and reacting for 4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demolding to obtain a polyurethane composite material;
the preparation method of the modified basalt fiber comprises the following steps: 8g basalt fiber is dispersed in 150g of 60wt% ethanol water solution, then 2g of silane coupling agent KH550 is added into the solution, the solution is stirred and reacted for 2 hours at 65 ℃, and the modified basalt fiber is obtained after filtration, washing and drying.
Example 4
A preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing 5g of nano titanium dioxide in 150g of 80wt% ethanol water solution, adding 1.5g of vinyl trimethoxy silane into the solution, stirring the solution at 60 ℃ for reaction for 3 hours, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding 5g of nano titanium dioxide containing double bonds and 6g of 3-buten-1-ol into 150g of deionized water, uniformly mixing, then adding 0.8g of initiator benzoyl peroxide into the mixture, heating and stirring the mixture at 80 ℃ for reaction for 4 hours, and filtering, washing and drying the mixture after the reaction is completed to obtain modified nano titanium dioxide;
(3) Uniformly stirring 15g of polyoxypropylene glycol, 20g of modified nano titanium dioxide, 20g of 4,4' -dicyclohexylmethane diisocyanate and 0.8g of stannous octoate after vacuum dehydration, heating to 100 ℃ for reaction for 4 hours, then adding 15g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 6g of modified basalt fiber, 8g of triethylamine and 100g of acetone, stirring and reacting for 4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demoulding to obtain a polyurethane composite material;
the preparation method of the modified basalt fiber comprises the following steps: 6g basalt fiber is dispersed in 150g of 60wt% ethanol water solution, then 1.5g of silane coupling agent KH550 is added into the solution, the solution is stirred and reacted for 2 hours at 65 ℃, and the modified basalt fiber is obtained after filtration, washing and drying.
Comparative example 1
A preparation method of a polyurethane composite material comprises the following steps:
stirring 12g of tetrahydrofuran-propylene oxide copolymer glycol, 25g of nano titanium dioxide, 20g of dicyclohexylmethane diisocyanate and 0.8g of stannous octoate uniformly after vacuum dehydration, heating to 100 ℃ for reaction for 4 hours, then adding 20g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 8g of basalt fiber, 10g of triethylamine and 120g of acetone, stirring and reacting for 4 hours to obtain a mixed material, pouring the mixed material into a mould, standing and foaming, curing, and demoulding to obtain the polyurethane composite material.
Comparative example 2
A preparation method of a polyurethane composite material comprises the following steps:
(1) Dispersing 6g of nano titanium dioxide in 150g of 80wt% ethanol water solution, adding 2g of vinyl trimethoxy silane into the solution, stirring the solution at 50 ℃ for reaction for 3 hours, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding 6g of nano titanium dioxide containing double bonds and 5g of 3-buten-1-ol into 150g of deionized water, uniformly mixing, then adding 0.8g of initiator benzoyl peroxide into the mixture, heating and stirring the mixture at 80 ℃ for reaction for 3 hours, and filtering, washing and drying the mixture after the reaction is completed to obtain modified nano titanium dioxide;
(3) Stirring 12g of tetrahydrofuran-propylene oxide copolymer glycol, 25g of modified nano titanium dioxide, 20g of dicyclohexylmethane diisocyanate and 0.8g of stannous octoate uniformly after vacuum dehydration, heating to 100 ℃ for reaction for 4 hours, then adding 20g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 8g of basalt fiber, 10g of triethylamine and 120g of acetone, stirring for reaction for 4 hours, obtaining a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demoulding to obtain the polyurethane composite material.
Comparative example 3
A preparation method of a polyurethane composite material comprises the following steps:
stirring 12g of tetrahydrofuran-propylene oxide copolymer glycol, 25g of nano titanium dioxide, 20g of dicyclohexylmethane diisocyanate and 0.8g of stannous octoate uniformly after vacuum dehydration, heating to 100 ℃ for reaction for 4 hours, then adding 20g of chain extender dimethylolpropionic acid, reacting for 3 hours at 120 ℃, then cooling to 40 ℃, adding 8g of modified basalt fiber, 10g of triethylamine and 120g of acetone, stirring and reacting for 4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demoulding to obtain a polyurethane composite material;
the preparation method of the modified basalt fiber comprises the following steps: 8g basalt fiber is dispersed in 150g of 60wt% ethanol water solution, then 2g of silane coupling agent KH550 is added into the solution, the solution is stirred and reacted for 2 hours at 65 ℃, and the modified basalt fiber is obtained after filtration, washing and drying.
The polyurethane composites prepared in examples 1-4 and comparative examples 1-3 were subjected to performance testing as follows:
tensile strength test: the method is carried out according to the GB/T528-2009 standard, the thickness of a test sample is 4mm, the stretching speed is 5mm/min, the test is carried out in parallel for three times, and the result is averaged;
hardness testing: the press-in hardness test method of vulcanized rubber or thermoplastic rubber according to GB/T531.1-2008 part 1: testing the Shore hardness standard, taking 3 test points on the same sample, and taking an average value of the results;
DI N wear: testing according to the standard of GB/T9867-2008 vulcanized rubber or thermoplastic rubber for measuring wear resistance (rotating roller type abrasion machine method), testing for three times, and taking an average value of the results; the test results are shown in table 1 below:
TABLE 1
Ultraviolet aging resistance test: samples prepared in examples 1-4 and comparative examples 1-3 were placed on a sample holder in an ultraviolet aging oven, and aging conditions were set: the temperature is 50 ℃, and the light intensity is 1w/m 2 The light source type was UVA-340nm, the sample was exposed for 168 hours under this condition, and the tensile strength and hardness of the sample were retested, and the test results are shown in Table 2:
TABLE 2
| Tensile Strength (MPa) | Shore hardness (A) | |
| Example 1 | 48.2 | 94 |
| Example 2 | 51.3 | 95 |
| Example 3 | 48.7 | 93 |
| Example 4 | 50.6 | 95 |
| Comparative example 1 | 23.4 | 72 |
| Comparative example 2 | 37.7 | 81 |
| Comparative example 3 | 32.5 | 79 |
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the polyurethane composite material is characterized by comprising the following steps of:
(1) Dispersing nano titanium dioxide in ethanol water solution, adding vinyl trimethoxy silane into the solution, stirring the solution for reaction, and filtering, washing and drying the solution after the reaction is completed to obtain double bond-containing nano titanium dioxide;
(2) Adding double bond-containing nano titanium dioxide and 3-butene-1-ol into deionized water, uniformly mixing, adding an initiator benzoyl peroxide into the mixture, heating and stirring for reaction, and filtering, washing and drying after the reaction is completed to obtain modified nano titanium dioxide;
(3) Uniformly stirring polyether polyol, modified nano titanium dioxide, diisocyanate and stannous octoate after vacuum dehydration, heating to 90-110 ℃ for reaction for 2-4 hours, then adding chain extender dimethylolpropionic acid, reacting for 3-5 hours at 100-120 ℃, then cooling to 30-40 ℃, adding modified basalt fiber, triethylamine and acetone, stirring for reaction for 3-4 hours to obtain a mixed material, pouring the mixed material into a mould, standing for foaming, curing, and demoulding to obtain the polyurethane composite material.
2. The method for preparing a polyurethane composite material according to claim 1, wherein in the step (1), the mass ratio of the nano titanium dioxide to the vinyl trimethoxysilane is 5-8:1-2.
3. The method for producing a polyurethane composite material according to claim 1, wherein in the step (1), the stirring reaction temperature is 40 to 60 ℃ and the stirring reaction time is 2 to 3 hours.
4. The method for producing a polyurethane composite material according to claim 1, wherein in the step (2), the mass ratio of the nano titanium dioxide containing double bonds, 3-butene-1-ol and benzoyl peroxide is 4-8:4-6:0.6-0.8.
5. The method for producing a polyurethane composite material according to claim 1, wherein in the step (2), the reaction temperature of heating and stirring is 60 to 80 ℃ and the reaction time of heating and stirring is 2 to 4 hours.
6. The method for preparing the polyurethane composite material according to claim 1, wherein in the step (3), the mass ratio of the polyether polyol, the modified nano titanium dioxide, the diisocyanate, the stannous octoate, the dimethylolpropionic acid, the modified basalt fiber, the triethylamine and the acetone is 10-15:15-25:10-20:0.5-1:10-20:5-10:6-10:80-120, wherein the polyether polyol is one or more of polyoxypropylene glycol, polytetrahydrofuran glycol and tetrahydrofuran-propylene oxide copolymer glycol, and the diisocyanate is one or more of hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
7. The method for producing a polyurethane composite material according to claim 1, wherein in the step (3), the method for producing the modified basalt fiber is as follows: dispersing basalt fiber in ethanol water solution, adding silane coupling agent KH550, stirring at 60-70 ℃ for reaction for 1-2h, filtering, washing and drying to obtain modified basalt fiber.
8. The method for preparing the polyurethane composite material according to claim 7, wherein the mass ratio of basalt fiber to silane coupling agent KH550 is 5-10:1-2.
9. A polyurethane composite material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the polyurethane composite according to claim 9 in a cable protective sheath.
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