CN107778733B - Composite material of isobutene/alkylstyrene polymer and fluororubber and preparation method thereof - Google Patents
Composite material of isobutene/alkylstyrene polymer and fluororubber and preparation method thereof Download PDFInfo
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- CN107778733B CN107778733B CN201610719960.2A CN201610719960A CN107778733B CN 107778733 B CN107778733 B CN 107778733B CN 201610719960 A CN201610719960 A CN 201610719960A CN 107778733 B CN107778733 B CN 107778733B
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- isobutylene
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 25
- 229910021389 graphene Inorganic materials 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 22
- 238000004073 vulcanization Methods 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 19
- 239000007921 spray Substances 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- -1 alkyl styrene Chemical compound 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 11
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 11
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims description 11
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003801 milling Methods 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 11
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012190 activator Substances 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 claims description 2
- XHUZSRRCICJJCN-UHFFFAOYSA-N 1-ethenyl-3-ethylbenzene Chemical compound CCC1=CC=CC(C=C)=C1 XHUZSRRCICJJCN-UHFFFAOYSA-N 0.000 claims description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 238000007906 compression Methods 0.000 abstract description 2
- 230000006835 compression Effects 0.000 abstract description 2
- 239000003566 sealing material Substances 0.000 abstract description 2
- 230000032683 aging Effects 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009472 formulation Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910021538 borax Inorganic materials 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000010436 fluorite Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C08L27/12—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 fluorine atoms
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/04—Crosslinking with phenolic resin
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a composite material of isobutene/alkylstyrene polymer and fluororubber and a preparation method thereof, the composite material prepared by the method has the advantages that the Shore A is 50-70, the tensile strength is 9.0-18.0 MPa, the elongation at break is 250-400%, the ASTM3# standard oil resistance change rate is 6-13% in mass change rate, 8-15% in volume change rate, 13-20% in compression permanent deformation (× 70h at 120 ℃), the aging coefficient is K less than or equal to 0.135, the composite material has good oil resistance and aging resistance, and the service life of a sealing material is prolonged.
Description
Technical Field
The invention relates to the field of fluororubber composite materials and preparation thereof, in particular to an isobutylene/alkylstyrene polymer and fluororubber composite material and a preparation method thereof.
Background
The fluorine rubber (FKM) is a special synthetic polymer elastomer containing fluorine atoms on carbon atoms of a main chain or a side chain, has excellent high temperature resistance, oil resistance and chemical resistance, good physical and mechanical properties, weather resistance, electric insulation, radiation resistance and the like, is widely applied to the fields of aerospace, aviation, military industry, national defense, automobiles, petrochemical industry and the like, wherein 75% of the yield is used for manufacturing O-rings, sealing elements, oil pipes, electric circuit sheath gaskets and gasket materials. Although fluororubbers have many excellent properties, they have disadvantages such as poor molding flowability, easy compression set, poor compatibility between the raw rubber processing technique and the physical properties of vulcanized rubber, and the like. Therefore, composite materials were studied.
The lubricating material is prepared by adding 0.1-5 parts by weight of fatty acid monoamide to 100 parts by weight of fluororubber to prepare a fluororubber composition, the fluororubber composition has good mold release performance, the molded product obtained by vulcanizing and molding the composition is prepared by adding 100 parts by weight of a flame retardant, a sealing material, a vehicle.
JP19870107743 describes a new coating for a new fluoroelastomer material consisting of an organic substance (such as vegetable oil, polyvinyl chloride plasticizer, rubber blend or silicone oil process oil) mixed with borax (for example, except borax; hydrated alumina, magnesia, natural sand, quartz powder, fluorite, perlite) and the like. JP2011063133(a) describes a luminescent sheet comprising a fluorine-containing rubber, which has a good luminescent effect over a long period of time, mainly by blending a luminescent material with or depositing a luminescent material on the rubber or plastic, and making the mixture into a sheet. JP2011063133(a) and JP5336313(B2) design a new rubber product by improving the interaction between organic molecules and inorganic compounds, and the raw material comprises fluorine rubber. GB1438404(A) describes gypsum containing fluororubber and possibly inorganic fillers, such as bauxite, fluorite, cryolite, graphite, quartz, flint, sand, sulphur, boron, aluminium profiles, borax, fine shale, aluminium, sillimanite, agalmatolite and the like. KR20100029345(a) provides a far infrared ray radiation pad which maintains infrared cushioning. The structure is as follows: 35-40 w% of silicon oxide, 23-28 w% of feldspar oxide, 25-29 w% of borax, 0.2-0.8 w% of boric acid, 0.4-0.8 w% of cobalt, 1.5-2 w% of magnesium, 0.7-1.2 w% of selenium, 0.14-cryolite alumina, 0.19 w% of lithium, 1.5-2 w% of zircon, 0.3-0.8 w% of fluorite, 0.2-0.9 w% of porcelain color and the like, and the components are mixed, melted, solidified and crushed. The infrared powder-discharging mixed softening agent is selected from soft synthetic resin and silicon rubber or the ratio of 1:4 to 1: 8. Thereafter, the mixture is injection molded.
Disclosure of Invention
The invention aims to provide a composite material of an isobutene/alkylstyrene polymer and fluororubber and a preparation method thereof, and the prepared composite material has excellent sealing performance.
The composite material of the isobutene/alkylstyrene polymer and the fluororubber comprises the following components in parts by weight based on 100 parts of the total mass of the isobutene/alkylstyrene polymer and the fluororubber: 30-45 parts of isobutene/alkylstyrene polymer, 55-70 parts of fluororubber, 2.5-8.0 parts of vulcanizing agent, 1-4 parts of vulcanization accelerator, 0.5-2 parts of silane coupling agent, 6-14 parts of plasticizer, 2-9 parts of activating agent and 30-60 parts of filler.
The invention also provides a preparation method of the composite material of the isobutene/alkylstyrene polymer and the fluororubber, which comprises the following steps: adding isobutene/alkylstyrene polymer, fluororubber, filler and silane coupling agent into an open mill, open milling for 3-10 min at 20-40 ℃, heating to 40-80 ℃, adding plasticizer, activator and vulcanizing agent, mixing for 2-10 min, adding vulcanization accelerator, continuously mixing for 2-6 min, thinly passing through a lower sheet to obtain a mixed material, and vulcanizing for 20 min-1 h under the vulcanization condition of 150-180 ℃ and 9-15 MPa to obtain the isobutene/alkylstyrene polymer and fluororubber composite material.
According to the preparation method of the isobutylene/alkylstyrene polymer and fluororubber composite material, the filler can be added again before the sheet is thin-passed, the added filler is preferably graphene oxide, and the adding amount is 5-10 parts.
The isobutene/alkylstyrene polymer is an isobutene/(C3-C12) styrene polymer, such as an isobutene/o-methylstyrene polymer, an isobutene/m-methylstyrene polymer, an isobutene/p-methylstyrene polymer, an isobutene/o-ethylstyrene polymer, an isobutene/m-ethylstyrene polymer, an isobutene/p-ethylstyrene polymer and the like.
The vulcanizing agent, the vulcanization accelerator, the silane coupling agent, the plasticizer, the activator and the filler are all common auxiliary agents in the field, and specific varieties and dosage can be selected according to common general knowledge of technicians in the field.
The vulcanizing agents are 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and phenolic resin, and the dosage of the vulcanizing agents is 0.5-1 part and 2-7 parts respectively.
The vulcanization accelerator is TETD or CZ or a mixture thereof.
The silane coupling agent is one or a mixture of KH-560 and KH-602.
The plasticizer is one or more of polytetrafluoroethylene, phthalate, isophthalate and citrate.
The activating agent is one or more of zinc stearate, zinc oxide and triethanolamine.
The filler is one or more of spray carbon black, graphene oxide and carbon nano tubes.
The roll spacing of the open mill is 0.5-1 mm.
The number of the thin pass is 3-5.
The parts are all parts by mass.
The molecular chain of the isobutylene/alkylstyrene polymer is saturated, the isobutylene/alkylstyrene polymer is not easy to vulcanize in the processing process, and the carbon atoms of the main chain or the side chain of the fluororubber contain fluorine atoms, so that the fluororubber is compounded with the isobutylene/alkylstyrene polymer, the processing and vulcanizing characteristics of the polymer are greatly improved.
Detailed Description
The present invention is further described below with reference to examples. It should be noted that the following examples are not intended to limit the scope of the present invention, and any modifications made on the basis of the present invention do not depart from the spirit of the present invention.
The required medicines are all commercial industrial products.
Test methods and standards: mooney viscosity: SH/T1232.1-2000 roll-through method; 300% stress at definite elongation, tensile strength, elongation at break: SH/T1600-2004, procedure 1ASTM IRB NO7 carbon Black, GB/T528-2009, type 1 cutter; oil resistance: GB/T1690-2006.
Example 1
The temperature of an open mill is raised to 20 ℃, the roller distance is adjusted to lmm, 30 parts of isobutylene/o-methylstyrene polymer, 70 parts of fluororubber, 40 parts of spray carbon black and graphene oxide (the mass ratio of the spray carbon black to the graphene oxide is 1:1) and 1 part of KH-560 silane coupling agent are added for open milling for 6min, the temperature is raised to 70 ℃, 6 parts of polytetrafluoroethylene and 3 parts of phthalate are added, 5 parts of zinc stearate, 2 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24023 parts of phenolic tackifying resin, mixing for 5min, adding 1 part of vulcanization accelerator TETD, continuing to mix for 6min, finally adding 1 part of graphene oxide, mixing for 8min, 3 times respectively for a left 3/4 cutter and a right 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing through for 5 times to obtain a mixed material, and vulcanizing for 30min under the vulcanization condition of 170 ℃ and 15MPa to obtain the composite material of the isobutylene/o-methylstyrene polymer and the fluororubber.
Comparative example 1
The test formulation and conditions were the same as in example 1 except that 30 parts of isobutylene/o-methylstyrene polymer was not added.
Example 2
The temperature of an open mill is raised to 40 ℃, the roller distance is adjusted to lmm, 35 parts of isobutylene/m-methylstyrene polymer, 65 parts of fluororubber, 50 parts of spray carbon black and carbon nano tube (the mass ratio of the spray carbon black to the carbon nano tube is 1:1) and 2 parts of KH-560 silane coupling agent are added for open milling for 3min, the temperature is raised to 50 ℃, 6 parts of polytetrafluoroethylene and 4 parts of zinc stearate are added, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24024 parts of phenolic tackifying resin, mixing for 6min, adding 2 parts of accelerator TETD, continuing mixing for 6min, finally adding 1.5 parts of graphene oxide, mixing for 4min, 3 times respectively for a left 3/4 cutter and a right 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing for 5 times to obtain a mixed material, and vulcanizing for 30min under the vulcanization condition of 160 ℃ and 12MPa to obtain the composite material of the isobutylene/m-methylstyrene polymer and the fluororubber.
Comparative example 2
The test formulation and conditions were the same as in example 2 except that 35 parts of isobutylene/m-methylstyrene polymer was not added.
Example 3
The temperature of an open mill is raised to 30 ℃, the roller distance is adjusted to lmm, 40 parts of isobutylene/p-methylstyrene polymer, 60 parts of fluororubber, 50 parts of spray carbon black, 50 parts of graphene oxide and carbon nano tube (the mass ratio of the spray carbon black, the graphene oxide and the carbon nano tube is 1:1:1) and 2 parts of KH-560 silane coupling agent are added for open milling for 5min, the temperature is raised to 60 ℃, 7 parts of polytetrafluoroethylene are added, 5 parts of zinc stearate, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24026 parts of phenolic tackifying resin, mixing for 10min, adding 1 parts of accelerator TETD, continuing mixing for 2min, finally adding 0.5 part of graphene oxide, mixing for 3min, mixing 3 times respectively by a left 3/4 cutter and a right 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing through for 5 times to obtain a mixed material, and vulcanizing for 1h under the vulcanization condition of 150 ℃ and 10MPa to obtain the composite material of the isobutylene/p-methylstyrene polymer and the fluororubber.
Comparative example 3
The test formulation and conditions were the same as in example 3 except that 40 parts of isobutylene/para-methylstyrene polymer was not added.
Example 4
The temperature of an open mill is raised to 40 ℃, the roller distance is adjusted to lmm, 45 parts of isobutylene/p-methylstyrene polymer, 55 parts of fluororubber, 50 parts of spray carbon black, 50 parts of graphene oxide and carbon nano tube (the mass ratio of the spray carbon black to the graphene oxide to the carbon nano tube is 1:2:1) and 1 part of KH-560 silane coupling agent are added for open milling for 3min, the temperature is raised to 80 ℃, 8 parts of polytetrafluoroethylene are added, 3 parts of zinc stearate, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24025 parts of phenolic tackifying resin, mixing for 5min, adding 2 parts of accelerator TETD, continuing mixing for 5min, finally adding 1.0 part of graphene oxide, mixing for 5min, respectively 3 times by a left cutter and a right cutter 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing through for 5 times to obtain a mixed material, and vulcanizing for 30min under the vulcanization condition of 170 ℃ and 12MPa to obtain the composite material of the isobutylene/p-methylstyrene polymer and the fluororubber.
Comparative example 4
The test formulation and conditions were the same as in example 4 except that 45 parts of isobutylene/para-methylstyrene polymer was not added.
Example 5
The temperature of an open mill is raised to 30 ℃, the roller distance is adjusted to lmm, 35 parts of isobutylene/o-methylstyrene polymer, 65 parts of fluororubber, 50 parts of spray carbon black and graphene oxide (the mass ratio of the spray carbon black to the graphene oxide is 1:2) and 1.5 parts of KH-560 silane coupling agent are added for open milling for 6min, the temperature is raised to 80 ℃, 8 parts of polytetrafluoroethylene and 5 parts of zinc stearate are added, 2 parts of zinc oxide, 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24022 parts of phenolic tackifying resin, mixing for 6min, adding a promoter TETD1 parts, continuing mixing for 3min, finally adding 1.5 parts of graphene oxide, mixing for 8min, 3 times respectively for a left 3/4 cutter and a right 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing through for 5 times to obtain a mixed material, and vulcanizing for 30min under the vulcanization condition of 160 ℃ and 15MPa to obtain the composite material of the isobutylene/o-methylstyrene polymer and the fluororubber.
Comparative example 5
The test formulation and conditions were the same as in example 5 except that 35 parts of isobutylene and o-methylstyrene polymer were not added.
Example 6
The temperature of an open mill is raised to 20 ℃, the roller distance is adjusted to lmm, 45 parts of isobutylene/m-methylstyrene polymer, 55 parts of fluororubber, 50 parts of spray carbon black and carbon nano tube (the mass ratio of the spray carbon black to the carbon nano tube is 1:2) and 2 parts of KH-560 silane coupling agent are added for open milling for 6min, the temperature is raised to 50 ℃, 10 parts of polytetrafluoroethylene and 3 parts of zinc stearate are added, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 24026 parts of phenolic tackifying resin, mixing for 6min, adding 1 part of accelerator TETD, continuing mixing for 6min, finally adding 1.0 part of graphene oxide, mixing for 8min, 3 times respectively for a left 3/4 cutter and a right 3/4 cutter, adjusting the roller distance to 0.5mm, thinly passing for 5 times to obtain a mixed material, and vulcanizing for 30min under the vulcanization condition of 180 ℃ and 10MPa to obtain the composite material of the isobutylene/m-methylstyrene polymer and the fluororubber.
Comparative example 6
The test formulation and conditions were the same as in example 6 except that no 45 parts of isobutylene/m-methylstyrene polymer was added.
Example 7
The temperature of an open mill is raised to 20 ℃, the roller distance is adjusted to lmm, 35 parts of isobutylene/o-methylstyrene polymer, 65 parts of fluororubber, 40 parts of spray carbon black and graphene oxide (the mass ratio of the spray carbon black to the graphene oxide is 1:1) and 2 parts of KH-560 silane coupling agent are added for open milling for 6min, the temperature is raised to 70 ℃, 6 parts of polytetrafluoroethylene and 3 parts of phthalate are added, 5 parts of zinc stearate, 2 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and 24023 parts of phenolic tackifying resin are mixed for 5min, 1 part of vulcanization accelerator TETD is added to be continuously mixed for 6min, the left and right 3/4 cutters are respectively mixed for 3 times, the roller distance is adjusted to 0.5mm, the materials are thinly passed through for 5 times and are sliced to obtain mixed materials, and then the mixed materials are vulcanized for 30min under the vulcanization condition of 170 ℃ and 15MPa, so that the composite material of the isobutylene/o-methylstyrene polymer and the fluororubber is obtained.
Comparative example 7
The test formulation and conditions were the same as in example 7 except that 35 parts of isobutylene/o-methylstyrene polymer was not added.
Example 8
The temperature of an open mill is raised to 40 ℃, the roller distance is adjusted to lmm, 40 parts of isobutylene/m-methylstyrene polymer, 60 parts of fluororubber, 50 parts of spray carbon black, 50 parts of graphene oxide and carbon nano tube (the mass ratio of the spray carbon black to the graphene oxide to the carbon nano tube is 1:1:1) and 2 parts of KH-560 silane coupling agent are added for open milling for 3min, the temperature is raised to 50 ℃, 6 parts of polytetrafluoroethylene are added, 4 parts of zinc stearate, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and 24024 parts of phenolic tackifying resin are mixed for 6min, 2 parts of accelerator TETD are added to be continuously mixed for 6min, the left and right 3/4 cutters are respectively mixed for 3 times, the roller distance is adjusted to 0.5mm, the mixture is obtained by thin passing for 5 times and then is vulcanized for 30min under the vulcanization condition of 170 ℃ and 12MPa, and the composite material of the isobutylene/m-methylstyrene polymer and the fluororubber is obtained.
Comparative example 8
The test formulation and conditions were the same as in example 8 except that 40 parts of isobutylene/m-methylstyrene polymer was not added.
Example 9
The open mill is heated to 30 ℃, the roller distance is adjusted to lmm, 35 parts of isobutylene/p-methylstyrene polymer, 65 parts of fluororubber, 50 parts of graphene oxide and carbon nano tube (the mass ratio of the graphene oxide to the carbon nano tube is 1:1), 2 parts of KH-560 silane coupling agent are added for open milling for 5min, the temperature is increased to 60 ℃, 7 parts of polytetrafluoroethylene, 5 parts of zinc stearate, 3 parts of zinc oxide, 0.5 part of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and 24026 parts of phenolic tackifying resin are added for mixing for 10min, then the accelerant TETD1 is added for mixing for 2min, 3 times are respectively carried out on a left cutter and a right cutter 3/4, the roller distance is adjusted to 0.5mm, the mixture is obtained by thin passing for 5 times, and then the mixture is vulcanized for 1h under the vulcanization condition of 160 ℃ and 10MPa, and the isobutylene/p-methylstyrene polymer and fluororubber composite is obtained.
Comparative example 9
The test formulation and conditions were the same as in example 9 except that 35 parts of isobutylene/para-methylstyrene polymer was not added.
TABLE 1 Properties of composites obtained in examples and comparative examples
Claims (11)
1. The composite material of the isobutene/alkyl styrene polymer and the fluororubber is characterized by comprising the following components in parts by weight based on 100 parts of the total mass of the isobutene/alkyl styrene polymer and the fluororubber: 30-45 parts of isobutene/alkyl styrene polymer, 55-70 parts of fluororubber, 2.5-8.0 parts of vulcanizing agent, 1-4 parts of vulcanization accelerator, 0.5-2 parts of silane coupling agent, 6-14 parts of plasticizer, 2-9 parts of activating agent and 30-60 parts of filler,
wherein the isobutylene/alkylstyrene polymer is an isobutylene/o-methylstyrene polymer, an isobutylene/m-methylstyrene polymer, an isobutylene/p-methylstyrene polymer, an isobutylene/o-ethylstyrene polymer, an isobutylene/m-ethylstyrene polymer, or an isobutylene/p-ethylstyrene polymer, and
the vulcanizing agents are 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and phenolic resin, and the using amounts of the vulcanizing agents are 0.5-1 part and 2-7 parts respectively.
2. Composite material according to claim 1, characterized in that the vulcanization accelerator is one of the accelerators TETD, CZ or mixtures thereof.
3. The composite material of claim 1, wherein the silane coupling agent is selected from the group consisting of KH-560, KH-602, and mixtures thereof.
4. The composite material of claim 1, wherein the plasticizer is one or more of polytetrafluoroethylene, phthalate, isophthalate, and citrate.
5. The composite material of claim 1, wherein the activator is one or more of zinc stearate, zinc oxide, and triethanolamine.
6. The composite material of claim 1, wherein the filler is one or more of spray carbon black, graphene oxide, and carbon nanotubes.
7. A method for preparing the isobutylene/alkylstyrene polymer and fluororubber composite according to claim 1, comprising the steps of: adding isobutene/alkylstyrene polymer, fluororubber, filler and silane coupling agent into an open mill, open milling for 3-10 min at 20-40 ℃, heating to 40-80 ℃, adding plasticizer, activator and vulcanizing agent, mixing for 2-10 min, adding vulcanization accelerator, continuously mixing for 2-6 min, thinly passing through a lower sheet to obtain a mixed material, and vulcanizing for 20 min-1 h under the vulcanization condition of 150-180 ℃ and 9-15 MPa to obtain the isobutene/alkylstyrene polymer and fluororubber composite material.
8. The method according to claim 7, wherein the filler is further added and kneaded for 3 to 6 minutes before the sheet is drawn down, and the amount of the filler added is 0.5 to 5 parts by weight based on the total amount of the filler.
9. The method according to claim 8, wherein the filler is graphene oxide.
10. The preparation method of claim 7, wherein the roll gap of the open mill is 0.5-1 mm.
11. The method according to claim 7, wherein the number of thin passes is 3 to 5.
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CN104602911A (en) * | 2012-09-06 | 2015-05-06 | 埃克森美孚化学专利公司 | Construction comprising tie layer |
CN104619520A (en) * | 2012-09-12 | 2015-05-13 | 住友电木株式会社 | Tire inner liner sheet and tire |
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US6013218A (en) * | 1994-09-28 | 2000-01-11 | The Goodyear Tire & Rubber Company | Tire cure bladders cured with brominated phenolic resigns and containing PTFE and/or graphite |
CN1631661A (en) * | 1994-09-30 | 2005-06-29 | 固特异轮胎和橡胶公司 | Tire curing bladder containing polytetrafluoroethylene powder |
CN104487357A (en) * | 2012-06-08 | 2015-04-01 | 诺玛科公司 | Closure for a product-retaining container |
CN104602911A (en) * | 2012-09-06 | 2015-05-06 | 埃克森美孚化学专利公司 | Construction comprising tie layer |
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