CN117362873A - Preparation method of perfluoroether elastomer composition - Google Patents
Preparation method of perfluoroether elastomer composition Download PDFInfo
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- CN117362873A CN117362873A CN202311147508.XA CN202311147508A CN117362873A CN 117362873 A CN117362873 A CN 117362873A CN 202311147508 A CN202311147508 A CN 202311147508A CN 117362873 A CN117362873 A CN 117362873A
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- perfluoroether
- graphene oxide
- reactor
- perfluoroether elastomer
- elastomer
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- 229920001774 Perfluoroether Polymers 0.000 title claims abstract description 181
- 229920001971 elastomer Polymers 0.000 title claims abstract description 166
- 239000000806 elastomer Substances 0.000 title claims abstract description 140
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 77
- 239000000839 emulsion Substances 0.000 claims abstract description 69
- 238000002156 mixing Methods 0.000 claims abstract description 51
- 238000004073 vulcanization Methods 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 36
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 36
- 239000012053 oil suspension Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 19
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000006096 absorbing agent Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 40
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 10
- HDDMREWZGLZQMX-UHFFFAOYSA-N azanium;carbonofluoridate Chemical compound [NH4+].[O-]C(F)=O HDDMREWZGLZQMX-UHFFFAOYSA-N 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- JILAKKYYZPDQBE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoro-1,4-diiodobutane Chemical compound FC(F)(I)C(F)(F)C(F)(F)C(F)(F)I JILAKKYYZPDQBE-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000001307 helium Substances 0.000 description 22
- 229910052734 helium Inorganic materials 0.000 description 22
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 22
- 239000011159 matrix material Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 7
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 7
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000004593 Epoxy Chemical group 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of a perfluoroether elastomer composition, which comprises the following steps: preparing a surface hydrophobically modified graphene oxide fluoroether oil suspension; reacting the graphene oxide fluoroether oil suspension, deoxidized deionized water, an emulsifier, a vulcanization point monomer, a chain transfer agent, a pH regulator, an initiator and a perfluoroether elastomer comonomer to prepare a perfluoroether elastomer emulsion containing graphene oxide; synthesizing PTFE emulsion; mixing and coprecipitating the perfluoroether elastomer emulsion and the PTFE emulsion under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer; and (3) mixing the perfluoroether elastomer with a vulcanizing agent, a vulcanization auxiliary agent, an acid absorber and graphene oxide thin tube to obtain a rubber compound, molding the rubber compound, and performing two-stage vulcanization to obtain the perfluoroether elastomer composition. The perfluoro ether elastomer composition prepared by the invention has the advantages of good gas barrier property and low permeability.
Description
Technical Field
The invention relates to the field of preparation of perfluoroether elastomers, in particular to a preparation method of a perfluoroether elastomer composition.
Background
Many of the corrosive or flammable compounds used in semiconductor manufacturing processes undergo complex processing to form toxic and hazardous gas mixtures that require a seal within the pipe prior to chemical absorption or the like and cannot leak. The sealing materials used are required to have excellent mechanical properties, stable chemical properties and high gas barrier properties.
Seal leakage is mainly in two forms, one is interface leakage: the structural surface is rough and deformed, the sealing gasket is not pressed, and the bolts are deformed; second, osmotic leakage: due to loose sealing material and poor compactness. Osmotic leakage is a major challenge to be solved, especially when helium is used as a tracer gas for leakage detection, and higher requirements are placed on the compactness of the sealing material. The high molecular polymer itself has permeability due to the multiplicity and creep properties of the constituent high molecular polymer units. The barrier property of the polymer material refers to the ability of the polymer material to block the penetration of small molecular substances such as water vapor, oxygen, carbon dioxide, organic molecules and the like. The barrier properties of the polymer materials depend on the types of small molecular substances that permeate, the structural properties of the polymer, the interactions between the polymer, and the external environmental conditions such as temperature and humidity. If the molecular segments and crystalline structures of the high molecular polymer are aligned and the packing density is large, the penetration of small molecular substances is difficult. The small molecular substances penetrate through the high molecular polymer mainly through the amorphous region and the crystal defect part of the high molecular polymer, and pinholes, defects, microcracks and the like of the polymer material can cause more small molecular substances to penetrate through the material, so that the gas barrier property of the material is reduced.
The gas permeation process of the polymeric material consists of three steps: physical adhesion of gas to the surface of the polymeric material, absorption of adhering gas molecules, and diffusion of gas in the polymeric material. Therefore, the addition of impermeable layered fillers to a polymer matrix, such as organic montmorillonite, mica flakes, graphene nanoplatelets, etc., which can form "nano-barrier walls" in the polymer matrix, thus altering the diffusion path of gas-permeable molecules in the polymer, allowing the diffusion molecules to follow a longer more tortuous path through the "nano-barrier walls", is an effective means of improving the gas barrier properties of the polymer material. The main factors affecting the bending of the penetration path of the diffusing molecules in this process are three: mass fraction of nanoplatelets, morphology of nanoplatelets, and specific surface area of nanoplatelets. Therefore, uniformly dispersed nano sheets with large specific surface area are ideal fillers for preparing high gas barrier materials.
Graphene Oxide (GO) is an Oxide of Graphene, which is brown yellow in color, and common products on the market are in powder, flake and solution forms. The oxidation reaction leads the surface of GO to have a plurality of oxygen-containing functional groups such as hydroxyl, carboxyl, epoxy, and the like, and is very suitable for carrying out functional modification on the GO, thereby improving the dispersibility of the GO in a polymer matrix, improving the compatibility with the polymer matrix, and further improving the comprehensive performance of the composite material. In addition, polytetrafluoroethylene (PTFE) is a resin material formed by copolymerizing tetrafluoroethylene, fluorine atoms on a molecular chain of the PTFE are orderly and tightly arranged, so that the PTFE has higher stability and crystallinity, after the fluorinated surface of GO is modified, the GO and the PTFE are mixed into a fluoroelastomer matrix by a blending method, and the permeability of gas to the fluoroelastomer composition can be remarkably reduced. However, the dispersibility of the modified GO in the matrix still has a certain limit, and further improvement on the addition mode of the GO in the matrix is needed, so that the dispersibility of the GO in the matrix is improved.
Based on the above, a new technical scheme is needed to solve the problem of dispersion of graphene oxide GO and PTFE in a fluorine-containing elastomer matrix, improve the gas barrier property of fluorine-containing rubber, reduce the permeability and widen the application of fluorine-containing rubber in the field of sealing materials.
Disclosure of Invention
In view of this, the present invention provides in a first aspect a process for the preparation of a perfluoroether elastomer composition, said process comprising the steps of:
a process for preparing a perfluoroether elastomer composition, said process comprising the steps of:
s1, dispersing a graphene oxide aqueous solution in a surfactant solution, separating to obtain surface hydrophobically modified graphene oxide, and dispersing the surface hydrophobically modified graphene oxide in fluoroether oil to obtain a surface hydrophobically modified graphene oxide fluoroether oil suspension;
s2, adding the graphene oxide fluoroether oil suspension into a reactor containing deoxidized deionized water, an emulsifier, a vulcanization point monomer, a chain transfer agent, a pH regulator, an initiator and a perfluoroether elastomer comonomer for reaction to prepare a perfluoroether elastomer emulsion containing graphene oxide;
s3, adding a perfluorocarboxylic acid ammonium salt dispersing agent aqueous solution, TFE monomers and an initiator into a reactor to synthesize PTFE emulsion;
s4, mixing and coprecipitating the perfluoroether elastomer emulsion prepared in the step S2 and the PTFE emulsion prepared in the step S3 under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing the perfluoroether elastomer with a vulcanizing agent, a vulcanization aid, an acid absorber and graphene oxide to obtain a rubber compound, molding the rubber compound, and performing two-stage vulcanization to obtain the perfluoroether elastomer composition.
Preferably, the surfactant in the S1 is a perfluorinated silane aqueous solution with the concentration of 1-2 wt%.
Preferably, the surfactant in S1 comprises heptadecafluorodecyl trimethoxysilane or perfluorodecyl triethoxysilane.
Preferably, the mass ratio of the surface hydrophobically modified graphene oxide to the fluoroether oil in S1 is 1.0: (1.0-2.0).
Preferably, the total addition amount of the graphene oxide in the S1 and the S5 is 5wt% to 20wt% of the mass of the perfluoroether elastomer comonomer in the S3, and the mass ratio of the graphene oxide in the S1 and the S5 is 1.0: (0.5-2.0).
Preferably, the fluoroether oil in S1 comprises CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF＝CF 2 And CF (compact F) 3 O(CF 2 O) m CF＝CF 2 Wherein n is 0 to 5 and m is 0 to 6.
Preferably, the specific step of S2 is:
s21, mixing an emulsifier, graphene oxide fluoroether oil suspension and deoxidized water according to the following proportion (25-32): (3-5): (65-70) heating to 40-60deg.C to form emulsion, and adding N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding a portion of the perfluoroether elastomer comonomer to raise the reactor pressure to 0.5MPa to 1.5MPa;
s22, adding 50-70% of deoxidized deionized water and a pH regulator into the reactor, increasing the temperature in the reactor to 80-90 ℃, and adding perfluoroether elastomer comonomer into the reactor to increase the pressure in the reactor to 2.0-5.0 MPa;
s23, adding an initiator, a vulcanization point monomer and a chain transfer agent into a reactor, and continuously adding a perfluoroether elastomer comonomer in the reaction process to maintain stable pressure so as to obtain a perfluoroether elastomer emulsion containing graphene oxide;
wherein the emulsifier in S21 is at least one of an ionic surfactant and a nonionic surfactant; the perfluoro ether elastomer comonomer comprises tetrafluoroethylene and perfluoroalkyl vinyl ether, and the adding mass ratio of the tetrafluoroethylene to the perfluoroalkyl vinyl ether is 1.0: (0.5-2.0); the initiator in the S23 comprises any one of sodium persulfate, potassium persulfate and ammonium persulfate; the vulcanization point monomer comprises any one of chlorotrifluoroethylene, chloroethylene, propylene, isobutene and a vulcanization part monomer containing bromine or iodine, wherein the vulcanization part monomer containing bromine or iodine comprises CF 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br, 1-bromo-2, 2-difluoroethylene, bromotrifluoroethylene, 4-bromo-1, 2-trifluorobutene-1, 2-bromoperfluoro (ethylvinyl) ether, 3-bromoperfluoro (propylvinyl) ether, and 4-iodo-3, 4-tetrafluorobutene; chain transfer agents include methanol, methyl formate, t-butyl acetate, methylene iodide, perfluoroalkyl iodide, and 1, 4-diiodoperfluoro-butaneAny one of (3); wherein the addition amounts of the chain transfer agent, the initiator and the vulcanization point monomer are respectively 0.01 to 3.0 weight percent, 0.05 to 0.5 weight percent and 0.5 to 5.0 weight percent of the mass of the perfluoroether elastomer comonomer.
Preferably, the specific step of S3 is: adding TFE monomer into a reactor containing perfluorocarboxylic acid ammonium salt dispersing agent aqueous solution, adding initiator persulfate at 0-90 ℃ and 0.3-2.4 MPa, and stirring to synthesize PTFE emulsion; wherein the mass ratio of the ammonium perfluor carboxylate dispersant, TFE monomer and initiator persulfate is (2.0-3.0): (20-40): (0.05-0.15).
Preferably, the mass ratio of the perfluoroether elastomer emulsion to the PTFE emulsion in the S4 is 100wt%:5wt% to 20wt%.
Preferably, the molding conditions in the step S5 are that the pressure is 8MPa-12MPa, the temperature is 160-175 ℃ and the time is 5-16 min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
In a second aspect, the present invention provides a process for preparing a perfluoroether elastomer composition, which is prepared by the process described above.
Compared with the prior art, the beneficial effects that above-mentioned at least one technical scheme that this description embodiment adopted can reach include at least:
(1) According to the invention, the surfactant heptadecafluorodecyl trimethoxy silane is adopted to modify graphene oxide, the hydrolysis speed of the heptadecafluorodecyl trimethoxy silane is faster than that of ethoxysilane, the efficiency is higher, low molecular weight alcohol is released after hydrolysis, and the generated active silanol can generate chemical bonding with hydroxyl, carboxyl and oxygen-containing groups in the graphene oxide, so that a self-assembled monomolecular fluorosilicon film layer is formed on the surface of an inorganic substance, and the treated graphene oxide has extremely low surface energy and excellent hydrophobic property;
(2) The graphene oxide is added in two different forms, namely, the perfluoroether elastomer emulsion is prepared by using a graphene oxide fluoroether oil suspension, and is added during coprecipitation; secondly, adding graphene oxide during thin-pass mixing; the addition mode ensures that the graphene oxide is better dispersed in the polymer matrix, thereby improving the compatibility of the graphene oxide and the polymer matrix and improving the comprehensive performance of the composite material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a helium detector detection flow.
Wherein, 01: a helium atmosphere tank; 011: a seal ring; 012: a backing ring; 013: a bolt fastener; 014a, 014b: a flange; 02: a helium leak detector; 03: a vacuum system; 013a, 013b, 013c: a vacuum valve; 013d: a three-way valve; 033: a pressure gauge; 04: a helium source; 05: high-low temperature environment box.
Detailed Description
Embodiments of the present application are described in detail below with reference to the accompanying drawings.
Other advantages and effects of the present application will become apparent to those skilled in the art from the present disclosure, when the following description of the embodiments is taken in conjunction with the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present application. The present application may be embodied or carried out in other specific embodiments, and the details of the present application may be modified or changed from various points of view and applications without departing from the spirit of the present application. It should be noted that the following embodiments and features in the embodiments may be combined with each other without conflict. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present application, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, apparatus may be implemented and/or methods practiced using any number and aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should also be noted that the illustrations provided in the following embodiments merely illustrate the basic concepts of the application by way of illustration, and only the components related to the application are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complicated.
In addition, in the following description, specific details are provided in order to provide a thorough understanding of the examples. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details.
Many of the corrosive or flammable compounds used in semiconductor manufacturing processes undergo complex processing to form toxic and hazardous gas mixtures that require a seal within the pipe prior to chemical absorption or the like and cannot leak. The sealing materials used are required to have excellent mechanical properties, stable chemical properties, and high gas barrier properties. After the GO is subjected to fluorinated surface modification, the GO and PTFE are mixed into the perfluoroether elastomer matrix, so that the gas permeability of the composite material can be remarkably reduced, however, the dispersibility of the modified GO in the matrix is still limited to a certain extent, so that the addition mode of the GO in the matrix needs to be further improved, and the dispersibility of the GO in the matrix is improved.
The invention provides a preparation method of a perfluoroether elastomer composition, which solves the problem of dispersion of graphene oxide GO and PTFE in a fluorine-containing elastomer matrix, improves the gas barrier property of fluorine-containing rubber, reduces the permeability and widens the application of the fluorine-containing rubber in the field of sealing materials.
Based on the above, the invention provides a preparation method of the perfluoroether elastomer composition, wherein graphene oxide is added in two different forms in the preparation process of the perfluoroether elastomer composition, so that the dispersibility of the perfluoroether elastomer composition in a base material and the gas barrier performance of the perfluoroether elastomer composition are improved.
The following describes the technical solutions provided by the embodiments of the present application with reference to the accompanying drawings.
The present invention provides in a first aspect a process for the preparation of a perfluoroether elastomer composition, said process comprising the steps of:
s1, dispersing a graphene oxide aqueous solution in a surfactant solution, separating to obtain surface hydrophobically modified graphene oxide, and dispersing the surface hydrophobically modified graphene oxide in fluoroether oil to obtain a surface hydrophobically modified graphene oxide fluoroether oil suspension;
s2, adding the graphene oxide fluoroether oil suspension into a reactor containing deoxidized deionized water, an emulsifier, a vulcanization point monomer, a chain transfer agent, a pH regulator, an initiator and a perfluoroether elastomer comonomer for reaction to prepare a perfluoroether elastomer emulsion containing graphene oxide;
s3, adding a perfluorocarboxylic acid ammonium salt dispersing agent aqueous solution, TFE monomers and an initiator into a reactor to synthesize PTFE emulsion;
s4, mixing and coprecipitating the perfluoroether elastomer emulsion prepared in the step S2 and the PTFE emulsion prepared in the step S3 under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing the perfluoroether elastomer with a vulcanizing agent, a vulcanization aid, an acid absorber and graphene oxide to obtain a rubber compound, molding the rubber compound, and performing two-stage vulcanization to obtain the perfluoroether elastomer composition.
Preferably, the surfactant in the S1 is a perfluorinated silane aqueous solution with the concentration of 1-2 wt%.
Preferably, the surfactant in S1 comprises heptadecafluorodecyl trimethoxysilane or perfluorodecyl triethoxysilane.
In a second aspect, the present invention provides a perfluoroether elastomer composition prepared by the process described above.
Preferably, the mass ratio of the surface hydrophobically modified graphene oxide to the fluoroether oil in S1 is 1.0: (1.0-2.0).
Preferably, the total addition amount of the graphene oxide in the S1 and the S5 is 5wt% to 20wt% of the mass of the perfluoroether elastomer comonomer in the S3, and the mass ratio of the graphene oxide in the S1 and the S5 is 1.0: (0.5-2.0).
Preferably, the fluoroether oil in S1 comprises CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF＝CF 2 And CF (compact F) 3 O(CF 2 O) m CF＝CF 2 Wherein n is 0 to 5 and m is 0 to 6.
Preferably, the specific step of S2 is:
s21, mixing an emulsifier, graphene oxide fluoroether oil suspension and deoxidized water according to the following proportion (25-32): (3-5): (65-70) mixing uniformly, heating to 40-60 ℃ to form emulsion, and using N 2 Purging to make the oxygen content in the reactor less than 20ppm, and adding the perfluoroether elastomer comonomer into the stirred tank reactor to raise the pressure to 0.5-1.5 MPa;
s22, adding 50-70% of deoxidized deionized water and a pH regulator into the reactor, increasing the temperature in the reactor to 80-90 ℃, and adding perfluoroether elastomer comonomer into the reactor to increase the pressure in the reactor to 2.0-5.0 MPa;
s23, adding an initiator, a vulcanization point monomer and a chain transfer agent into a reactor, and continuously adding a perfluoroether elastomer comonomer in the reaction process to maintain stable pressure so as to obtain a perfluoroether elastomer emulsion containing graphene oxide;
wherein the emulsifier in S21 is at least one of an ionic surfactant and a nonionic surfactant; the perfluoroether elastomer comonomer comprises tetrafluoroethylene and perfluoroAlkyl vinyl ether, and the addition mass ratio of the alkyl vinyl ether and the alkyl vinyl ether is 1 (0.5-2); the initiator in the S23 comprises any one of sodium persulfate, potassium persulfate and ammonium persulfate; the vulcanization point monomer comprises any one of chlorotrifluoroethylene, chloroethylene, propylene, isobutene and a vulcanization part monomer containing bromine or iodine, wherein the vulcanization part monomer containing bromine or iodine comprises CF 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br, 1-bromo-2, 2-difluoroethylene, bromotrifluoroethylene, 4-bromo-1, 2-trifluorobutene-1, 2-bromoperfluoro (ethylvinyl) ether, 3-bromoperfluoro (propylvinyl) ether, and 4-iodo-3, 4-tetrafluorobutene; the chain transfer agent includes any one of methanol, methyl formate, t-butyl acetate, methylene iodide, perfluoroalkyl iodide, and 1, 4-diiodoperfluoro-butane; wherein the addition amounts of the chain transfer agent, the initiator and the vulcanization point monomer are respectively 0.01 to 3.0 weight percent, 0.05 to 0.5 weight percent and 0.5 to 5 weight percent of the mass of the perfluoroether elastomer comonomer.
Preferably, the specific step of S3 is: adding TFE monomer into a reactor containing perfluorocarboxylic acid ammonium salt dispersing agent, adding initiator persulfate into the reactor at the pressure of 0.3MPa-2.4MPa and the temperature of 0-90 ℃, and uniformly stirring to synthesize PTFE emulsion; wherein the mass ratio of the ammonium perfluor carboxylate dispersant, TFE monomer and initiator persulfate is (2.0-3.0): (20-40): (0.05-0.15).
Preferably, the mass ratio of the perfluoroether elastomer emulsion to the PTFE emulsion in the S4 is 100wt%: (5 wt% to 20 wt%).
Preferably, the molding conditions in the step S5 are that the pressure is 8MPa-12MPa, the temperature is 160-175 ℃ and the time is 5-16 min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
It should be understood that the following limitations on the type and amount of emulsifiers, cure site monomers, chain transfer agents, and molding and secondary curing conditions in the present invention are preferred embodiments and should not be construed as limiting the scope of the independent claims.
Specific examples are listed below:
example 1
S1, dispersing a graphene oxide aqueous solution in a heptadecafluorodecyl trimethoxy silane aqueous solution with the concentration of 1wt%, separating to obtain surface hydrophobically modified graphene oxide, and mixing 50g of the surface hydrophobically modified graphene oxide with 90g of fluoroether oil CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) 3 CF＝CF 2 Obtaining a graphene oxide fluoroether oil suspension with a hydrophobically modified surface through medium dispersion;
s21, mixing an emulsifier polyoxyethylene oleate, graphene oxide fluoroether oil suspension and deoxidized water according to a ratio of 25 in a 5L reactor: 10:65 mass ratio, heating to 40deg.C to form emulsion, and adding N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of mixed gas (36 wt%:59 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the stirred tank reactor to raise the pressure;
s22, adding 2.5L of deoxidized deionized water and 3gpH regulator disodium hydrogen phosphate into the reactor, heating the temperature in the reactor to 80 ℃, and continuously adding mixed gas (the proportion is 36wt%:59 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the reactor to increase the pressure in the reactor to 2.0MPa;
s23 adding 1.5g of initiator sodium persulfate and 15g of vulcanization point monomer CF into a reactor 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 1.5g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding mixed gas of perfluoroether elastomer comonomer TFE and PMVE in the reaction process to maintain stable pressure, and obtaining perfluoroether elastomer emulsion containing graphene oxide;
s3, adding 200g of TFE monomer into a reactor containing 6g of ammonium perfluorooctanoate aqueous solution, adding 0.1g of initiator potassium persulfate under the pressure of 2.3MPa and the temperature of 50 ℃, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 15wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC (total internal heat transfer) vulcanizing aid, 50g of a zinc oxide acid absorber and 50g of graphene oxide thin-way, obtaining a rubber compound, molding the rubber compound at the pressure of 8MPa and the temperature of 160 ℃ for 5min, and finally performing secondary vulcanization at the temperature of 200 ℃ for 10h to obtain the perfluoroether elastomer composition.
Example 2
S1, dispersing a graphene oxide aqueous solution in a heptadecafluorodecyl trimethoxy silane aqueous solution with the concentration of 1.5wt%, separating to obtain surface hydrophobically modified graphene oxide, and mixing 50g of the surface hydrophobically modified graphene oxide with 100g of fluoroether oil CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) 4 CF＝CF 2 Obtaining a graphene oxide fluoroether oil suspension with a hydrophobically modified surface through medium dispersion;
s21, mixing an emulsifier polyoxyethylene oleate, graphene oxide fluoroether oil suspension and deoxidized water in a 5L reactor according to the following steps of 28:4:68 by mass, heating to 40deg.C to form emulsion, and adding N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of mixed gas (36 wt%:59 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the stirred tank reactor to raise the pressure;
s22, adding 3L of deoxidized deionized water and 4.5gpH regulator disodium hydrogen phosphate into a reactor, heating the reactor to 80 ℃, and continuously adding mixed gas (the mass ratio is 36:59) of perfluoroether elastomer comonomer TFE and PMVE into the reactor to increase the pressure in the reactor to 2.0MPa;
s23 charging 2g of initiator potassium persulfate and 18g of vulcanization point monomer CF into a reactor 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 1.8g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding mixed gas of perfluoroether elastomer comonomer TFE and PMVE in the reaction process to maintain stable pressure, and obtaining perfluoroether elastomer emulsion containing graphene oxide;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorooctanoate aqueous solution, adding 0.2g of initiator potassium persulfate under the pressure of 2.5MPa and the temperature of 30 ℃, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 10wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC (total internal heat transfer) vulcanizing aid, 50g of acid absorber zinc oxide and 100g of graphene oxide in a thin way to obtain a mixed rubber, molding the mixed rubber at the pressure of 8MPa and the temperature of 160 ℃ for 10min, and finally performing secondary vulcanization at the temperature of 200 ℃ for 15h to obtain the perfluoroether elastomer composition.
Example 3
S1, dispersing a graphene oxide aqueous solution in a heptadecafluorodecyl trimethoxy silane aqueous solution with the concentration of 1.5wt%, separating to obtain surface hydrophobically modified graphene oxide, and mixing 80g of the surface hydrophobically modified graphene oxide with 140g of fluoroether oil CF 3 O(CF 2 O) 2 CF＝CF 2 Obtaining a graphene oxide fluoroether oil suspension with a hydrophobically modified surface through medium dispersion;
s21 emulsifier CF in a 5L reactor 3 CF 2 CF 2 O(CF 2 CF 2 O) 2 CF 2 COOH, graphene oxide fluoroether oil suspension and deoxygenated water according to 28:4:68 by mass, heating to 55deg.C to form emulsion, and mixing with N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of mixed gas (mass ratio of 35wt%:57 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the stirred tank reactor to raise the pressure;
s22, adding 3L of deoxidized deionized water and 4.5gpH regulator disodium hydrogen phosphate into a reactor, heating the temperature in the reactor to 85 ℃, and continuously adding perfluoroether elastomer comonomer TFE and PMVE mixed gas into the reactor to increase the pressure in the reactor to 4.0MPa;
s23, adding the mixed solution into a reactor, and adding 2g of initiator sodium persulfate and 20g of vulcanization point monomer CF 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 2g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding perfluoroether elastomer comonomer TFE and PMVE mixer in the reaction process to maintain stable pressure, thus obtaining perfluoroether elastomer emulsion containing graphene oxide;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorocarboxylate dispersing agent ammonium perfluorooctanoate, adding 0.2g of initiator persulfate at the temperature of 60 ℃ under the pressure of 2.5MPa, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 10wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC vulcanizing aid, 50g of acid absorber magnesium oxide and 50g of graphene oxide in a thin way to obtain a rubber compound, molding the rubber compound at the pressure of 10MPa and the temperature of 170 ℃ for 14min for molding, and finally performing secondary vulcanization at the temperature of 210 ℃ for 20h to obtain the perfluoroether elastomer composition.
Example 4
S1, dispersing a graphene oxide aqueous solution in a heptadecafluorodecyl trimethoxy silane aqueous solution with the concentration of 2wt%, separating to obtain surface hydrophobically modified graphene oxide, and mixing 120g of the surface hydrophobically modified graphene oxide with 220g of fluoroether oil CF 3 O(CF 2 O) 4 CF＝CF 2 Obtaining a graphene oxide fluoroether oil suspension with a hydrophobically modified surface through medium dispersion;
s21 emulsifier CF in a 5L reactor 3 CF 2 CF 2 O(CF 2 CF 2 O) 2 CF 2 COOH, graphene oxide fluoroether oil suspension and deoxygenated water according to 32:5:63 by mass ratio, heating to 60deg.C to form emulsion, and mixing with N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of mixed gas (mass ratio of 35wt%:53 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the stirred tank reactor to raise the pressure;
s22, adding 3.5L of deoxidized deionized water and 5gpH regulator disodium hydrogen phosphate into a reactor, regulating the oxygen content in the reactor to be less than 20ppm, increasing the temperature in the reactor to 90 ℃, and continuously adding mixed gas (mass ratio of 35wt%:53 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the reactor to increase the pressure in the reactor to 4.0MPa;
s23, in2g of initiator ammonium persulfate and 20g of vulcanization point monomer CF are added into the reactor 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 2g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding perfluoroether elastomer comonomer TFE and PMVE mixer in the reaction process to maintain stable pressure, thus obtaining perfluoroether elastomer emulsion containing graphene oxide fluoroether oil suspension;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorooctanoate serving as a perfluorocarboxylic acid ammonium salt dispersing agent, adding 0.3g of initiator ammonium persulfate under the pressure of 2.4MPa and the temperature of 90 ℃, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 10wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC vulcanizing aid, 50g of acid absorber magnesium oxide and 50g of graphene oxide in a thin way to obtain a rubber compound, molding the rubber compound at the pressure of 10MPa and the temperature of 170 ℃ for 14min for molding, and finally performing secondary vulcanization at the temperature of 200 ℃ for 20h to obtain the perfluoroether elastomer composition.
Comparative example 1
This comparative example differs from example 3 in that the graphene oxide in the graphene oxide fluoroether oil suspension and perfluoroether elastomer emulsion added at the time of coprecipitation is not modified, in particular:
s1, mixing 120g of graphene oxide with 220g of fluoroether oil CF 3 O(CF 2 O) 2 CF＝CF 2 Obtaining graphene oxide fluoroether oil suspension through medium dispersion;
s21 emulsifier CF in a 5L reactor 3 CF 2 CF 2 O(CF 2 CF 2 O) 2 CF 2 COOH, graphene oxide fluoroether oil suspension and deoxygenated water in a 28:4 ratio: 68 by mass, heating to 55deg.C to form emulsion, and mixing with N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of a mixture of perfluoroether elastomer comonomer TFE and PMVE (mass ratio of 35wt%:57 wt%) to the stirred tank reactor literPressing;
s22, adding 3L of deoxidized deionized water and 4.5gpH regulator disodium hydrogen phosphate into a reactor, regulating the oxygen content in the reactor to be less than 20ppm, raising the temperature in the reactor to 85 ℃, and continuously adding mixed gas (mass ratio of 35wt%:53 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the reactor to raise the pressure in the reactor to 4.0MPa;
s23, adding 2g of initiator ammonium persulfate and 20g of vulcanization point monomer CF into a reactor 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 2g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding perfluoroether elastomer comonomer TFE and PMVE mixer in the reaction process to maintain stable pressure, thus obtaining perfluoroether elastomer emulsion containing graphene oxide fluoroether oil suspension;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorooctanoate serving as a perfluorocarboxylic acid ammonium salt dispersing agent, adding 0.2g of initiator ammonium persulfate under the pressure of 2.5MPa and the temperature of 60 ℃, and stirring to synthesize PTFE emulsion;
s4, mixing and coprecipitating the perfluoroether elastomer emulsion prepared in the step S2 and the PTFE emulsion prepared in the step S3 under an acidic condition according to the mass ratio of 100wt% to 10wt%, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC vulcanizing aid, 50g of acid absorber magnesium oxide and 50g of graphene oxide in a thin way to obtain a rubber compound, molding the rubber compound at the pressure of 10MPa and the temperature of 170 ℃ for 14min for molding, and finally performing secondary vulcanization at the temperature of 200 ℃ for 20h to obtain the perfluoroether elastomer composition.
Comparative example 2
This comparative example differs from example 3 in that the perfluoroether elastomer emulsion added at the time of coprecipitation does not contain graphene oxide, in particular:
s11. emulsifier CF in a 5L reactor 3 CF 2 CF 2 O(CF 2 CF 2 O) 2 CF 2 COOH, graphene oxide fluoroether oil suspension and deoxygenated water according to 28:4:68 by mass, heating to 55deg.C to form emulsion, and mixing with N 2 PurgingAdding 500g of mixed gas (the mass ratio is 35wt%:57 wt%) of perfluoroether elastomer comonomer TFE and PMVE into a stirred tank reactor to boost pressure;
s22, adding 3L of deoxidized deionized water and 4.5gpH regulator disodium hydrogen phosphate into a reactor, regulating the oxygen content in the reactor to be less than 20ppm, raising the temperature in the reactor to 85 ℃, and continuously adding mixed gas (mass ratio of 35wt%:53 wt%) of perfluoroether elastomer comonomer TFE and PMVE into the reactor to raise the pressure in the reactor to 4.0MPa;
s23, adding 2g of initiator ammonium persulfate and 20g of vulcanization point monomer CF into a reactor 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 2g of chain transfer agent 1, 4-diiodoperfluoro-butane, and continuously adding perfluoroether elastomer comonomer TFE and PMVE mixer during the reaction to maintain stable pressure, thereby obtaining perfluoroether elastomer emulsion;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorooctanoate serving as a perfluorocarboxylic acid ammonium salt dispersing agent, adding 0.2g of initiator ammonium persulfate under the pressure of 2.5MPa and the temperature of 60 ℃, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 10wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC vulcanizing aid, 50g of acid absorber magnesium oxide and 50g of graphene oxide in a thin way to obtain a rubber compound, molding the rubber compound at the pressure of 10MPa and the temperature of 170 ℃ for 14min for molding, and finally performing secondary vulcanization at the temperature of 200 ℃ for 20h to obtain the perfluoroether elastomer composition.
Comparative example 3
The difference between this comparative example and example 3 is that graphene oxide is not added during the thin-pass kneading, and specifically:
s1, dispersing a graphene oxide aqueous solution in a heptadecafluorodecyl trimethoxy silane aqueous solution with the concentration of 1.5wt%, separating to obtain graphene oxide with a hydrophobically modified surface, and preparing 80g of oxygen with a hydrophobically modified surfaceGraphene oxide in 140g of fluoroether oil CF 3 O(CF 2 O) 2 CF＝CF 2 Obtaining a graphene oxide fluoroether oil suspension with a hydrophobically modified surface through medium dispersion;
s21 emulsifier CF in a 5L reactor 3 CF 2 CF 2 O(CF 2 CF 2 O) 2 CF 2 COOH, graphene oxide fluoroether oil suspension and deoxygenated water according to 28:4:68 by mass, heating to 55deg.C to form emulsion, and mixing with N 2 Purging to an oxygen content of less than 20ppm in the reactor, and adding 500g of mixed gas (mass ratio of 35wt%:57 wt%) of perfluoroether elastomer comonomer TFE and PMVE to the agitator reactor to raise the pressure;
s22, adding 3L of deoxidized deionized water and 4.5gpH regulator disodium hydrogen phosphate into a reactor, heating the temperature in the reactor to 85 ℃, and continuously adding perfluoroether elastomer comonomer TFE and PMVE mixed gas into the reactor to increase the pressure in the reactor to 4.0MPa;
s23, adding the mixed solution into a reactor, and adding 2g of initiator sodium persulfate and 20g of vulcanization point monomer CF 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br and 2g of chain transfer agent 1, 4-diiodoperfluoro-butane, continuously adding perfluoroether elastomer comonomer TFE and PMVE mixer in the reaction process to maintain stable pressure, thus obtaining perfluoroether elastomer emulsion containing graphene oxide;
s3, adding 200g of TFE monomer into a reactor containing 4g of ammonium perfluorocarboxylate dispersing agent ammonium perfluorooctanoate, adding 0.2g of initiator persulfate at the temperature of 60 ℃ under the pressure of 2.5MPa, and stirring to synthesize PTFE emulsion;
s4, according to the weight percentage of 100: mixing and coprecipitating the perfluoroether elastomer emulsion prepared by S2 and the PTFE emulsion prepared by S3 in a mass ratio of 10wt% under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing 1000g of the perfluoroether elastomer with 20g of a bis-dipentaerythritol vulcanizing agent, 40g of a TAIC (total internal heat transfer) vulcanizing aid and 50g of acid absorber magnesium oxide in a thin way to obtain a mixed rubber, molding the mixed rubber at the temperature of 170 ℃ for 14min under the pressure of 10MPa, and finally performing secondary vulcanization at the temperature of 210 ℃ for 20h to obtain the perfluoroether elastomer composition.
Helium leakage tests were carried out on the perfluoroether elastomer compositions prepared in examples 1 to 4 and comparative examples 1 to 3 using a helium meter, a seal ring 011 to be tested was placed between flanges 014a and 014b, 012 was used as a backing ring to play a limiting role, 013 was used as a bolt fastener, 015 was used as a temperature meter to measure the temperature of a helium atmosphere tank 01 and flange 014a connected to seal ring 011, the pressure of helium atmosphere tank 01 was measured by a pressure gauge 033, and a closed space 016 was connected to a vacuum system 03 and helium leak detector 02 via a vacuum valve set and a three-way valve. The vacuum valves 013a, 013b and 013c and the three-way valve were qualified by air tightness detection.
First, valve vacuum valves 031c and 031b are opened, 031a is closed, vacuum pump 03 is opened to draw vacuum, helium gas 04 is used for purging a helium atmosphere box, then valves 031c and 031b are closed, and helium gas is filled to enable the pressure of the helium atmosphere box 01 to reach 0.1MPa. The helium leak detector 02 is turned on, and the valve 031a and the tee 031d are opened to detect the concentration of helium gas in the closed space 016, and the helium leak rate is obtained from the change in the concentration of helium gas in the closed space 016.
Wherein, the temperature range: -60 ℃ -250 ℃; vacuum environment: 10 -3 -10 -6 Pa; minimum detectable leak rate: 5X 10 - 12 Pa·m 3 S; leak rate display range: 10 -3 -10 -12 Pa·m 3 S; the working medium is helium, different pressure difference environments can be set by adjusting the pressure of the external helium, and the test results are shown in table 1.
Table 1 helium leak detection of examples and comparative examples
Note that: p: pass (Pass test); f: fail (failed test), the standard for passing test is helium leak rate less than or equal to 1X 10 -9 Pa·m 3 /s。
As can be seen from the above data, the perfluoroether elastomer composition prepared according to the present invention has a low gas leakage rate, and the final gas leakage rate of examples 1 to 3 is 1X 10 -11 -6×10 -10 And as can be seen from examples 1-3,the perfluoroether elastomer composition prepared by the invention has good performance on gas barrier property and mechanical property when the hardness is moderate.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (11)
1. A process for preparing a perfluoroether elastomer composition, comprising the steps of:
s1, dispersing a graphene oxide aqueous solution in a surfactant solution, separating to obtain surface hydrophobically modified graphene oxide, and dispersing the surface hydrophobically modified graphene oxide in fluoroether oil to obtain a surface hydrophobically modified graphene oxide fluoroether oil suspension;
s2, adding the graphene oxide fluoroether oil suspension into a reactor containing deoxidized deionized water, an emulsifier, a vulcanization point monomer, a chain transfer agent, a pH regulator, an initiator and a perfluoroether elastomer comonomer for reaction to prepare a perfluoroether elastomer emulsion containing graphene oxide;
s3, adding a perfluorocarboxylic acid ammonium salt dispersing agent-containing aqueous solution, TFE monomers and an initiator into a reactor to synthesize PTFE emulsion;
s4, mixing and coprecipitating the perfluoroether elastomer emulsion prepared in the step S2 and the PTFE emulsion prepared in the step S3 under an acidic condition, washing, drying, and carrying out thin-pass mixing to obtain the perfluoroether elastomer;
s5, mixing the perfluoroether elastomer with a vulcanizing agent, a vulcanization aid, an acid absorber and graphene oxide to obtain a rubber compound, molding the rubber compound, and performing two-stage vulcanization to obtain the perfluoroether elastomer composition.
2. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the surfactant in S1 is an aqueous perfluorosilane solution having a concentration of 1wt% to 2 wt%.
3. A method of preparing a perfluoroether elastomer composition according to claim 2, wherein the surfactant in S1 comprises heptadecafluorodecyl trimethoxysilane or perfluorodecyl triethoxysilane.
4. The method for preparing the perfluoroether elastomer composition according to claim 1, wherein the mass ratio of the surface hydrophobically modified graphene oxide to the fluoroether oil in S1 is 1.0: (1.0-2.0).
5. The preparation method of the perfluoroether elastomer composition according to claim 1, wherein the total addition amount of graphene oxide in S1 and S5 is 5wt% to 20wt% of the mass of the perfluoroether elastomer comonomer in S3, and the mass ratio of graphene oxide in S1 and S5 is 1.0: (0.5-2.0).
6. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the fluoroether oil in S1 comprises CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF＝CF 2 And CF (compact F) 3 O(CF 2 O) m CF＝CF 2 Wherein n is 0 to 5 and m is 0 to 6.
7. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the specific step of S2 is:
s21, mixing and heating the emulsifier, the graphene oxide fluoroether oil suspension and deoxidized water according to the mass ratio of (25-32): 3-5): 65-70 to 40-60 ℃ to form emulsion, and using N 2 Purging to make the oxygen content in the reactor less than 20ppm, and adding part of the perfluoroether elastomer comonomer into the stirred tank reactor to raise the pressure to 0.5-1.5 MPa;
s22, adding 50-70% of deoxidized deionized water and a pH regulator into the reactor, increasing the temperature in the reactor to 80-90 ℃, and adding perfluoroether elastomer comonomer into the reactor to increase the pressure in the reactor to 2.0-5.0 MPa;
s23, adding an initiator, a vulcanization point monomer and a chain transfer agent into a reactor, and continuously adding a perfluoroether elastomer comonomer in the reaction process to maintain stable pressure so as to obtain a perfluoroether elastomer emulsion containing graphene oxide fluorine;
wherein the emulsifier in S21 is at least one of an ionic surfactant and a nonionic surfactant; the perfluoro ether elastomer comonomer comprises tetrafluoroethylene and perfluoroalkyl vinyl ether, and the adding mass ratio of the tetrafluoroethylene to the perfluoroalkyl vinyl ether is 1.0: (0.5-2.0); the initiator in the S23 comprises any one of sodium persulfate, potassium persulfate and ammonium persulfate; the vulcanization point monomer comprises any one of chlorotrifluoroethylene, chloroethylene, propylene, isobutene and a vulcanization part monomer containing bromine or iodine, wherein the vulcanization part monomer containing bromine or iodine comprises CF 2 ＝CFOCF 2 CF 2 CF 2 OCF 2 Br, 1-bromo-2, 2-difluoroethylene, bromotrifluoroethylene, 4-bromo-1, 2-trifluorobutene-1, 2-bromoperfluoro (ethylvinyl) ether, 3-bromoperfluoro (propylvinyl) ether, and 4-iodo-3, 4-tetrafluorobutene; the chain transfer agent includes any one of methanol, methyl formate, t-butyl acetate, methylene iodide, perfluoroalkyl iodide, and 1, 4-diiodoperfluoro-butane; wherein the addition amounts of the chain transfer agent, the initiator and the vulcanization point monomer are respectively 0.01 to 3.0 weight percent, 0.05 to 0.5 weight percent and 0.5 to 5.0 weight percent of the mass of the perfluoroether elastomer comonomer.
8. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the specific step of S3 is: adding TFE monomer into a reactor containing perfluorocarboxylic acid ammonium salt dispersing agent aqueous solution, adding initiator persulfate at 0-90 ℃ under the pressure of 0.3-2.4 MPa, and uniformly stirring to synthesize PTFE emulsion; wherein the mass ratio of the aqueous solution containing the perfluorocarboxylic acid ammonium salt dispersing agent to the TFE monomer to the initiator persulfate is (2.0-3.0): (20-40): (0.05-0.15).
9. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the mass ratio of the perfluoroether elastomer emulsion to the PTFE emulsion in S4 is 100: (5-20).
10. The method for preparing a perfluoroether elastomer composition according to claim 1, wherein the molding conditions in S5 are a pressure of 8MPa to 12MPa, a temperature of 160 ℃ to 175 ℃ and a time of 5min to 16min; the secondary vulcanization condition is that the temperature is 200-220 ℃ and the time is 10-24 hours.
11. A perfluoroether elastomer composition having high gas barrier properties, produced by the production method as claimed in any one of claims 1 to 10.
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