CN114479319A - Fluororubber compound and preparation method and application thereof - Google Patents
Fluororubber compound and preparation method and application thereof Download PDFInfo
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- CN114479319A CN114479319A CN202011172141.3A CN202011172141A CN114479319A CN 114479319 A CN114479319 A CN 114479319A CN 202011172141 A CN202011172141 A CN 202011172141A CN 114479319 A CN114479319 A CN 114479319A
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- fluororubber
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- rubber
- filler
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- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 91
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 68
- 239000005060 rubber Substances 0.000 claims abstract description 66
- 239000000945 filler Substances 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000004073 vulcanization Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 12
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 7
- 238000010008 shearing Methods 0.000 claims abstract description 4
- 239000006096 absorbing agent Substances 0.000 claims abstract description 3
- 239000010409 thin film Substances 0.000 claims abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 239000011737 fluorine Substances 0.000 claims description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 6
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 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 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 239000003921 oil Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004945 silicone rubber Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229920005560 fluorosilicone rubber Polymers 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- COVXBJIKNGVTNV-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;1,1-difluoroethene Chemical group FC(F)=C.FC(F)=C(F)Cl COVXBJIKNGVTNV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- -1 alkyl vinyl ether Chemical compound 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010720 hydraulic oil Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
The invention relates to the technical field of fluororubber, in particular to fluororubber compound and a preparation method and application thereof; the fluororubber gross rubber is prepared from the following raw materials in parts by weight: 100 parts of fluororubber modified raw rubber, 1.7-4.7 parts of vulcanization assistant and 10-40 parts of modified diatomite filler; the preparation method of the fluororubber compound comprises the following steps: (1) mixing an acid absorbing agent, a release agent and a reinforcing white filler to obtain a mixed auxiliary agent; (2) shearing and mixing a vulcanization aid and fluororubber modified raw rubber in an open mixing state, and then banburying; (3) adding the mixed auxiliary agent obtained in the step (1) and the modified diatomite filler into the banburied raw rubber, and then refining; (4) the thin film is passed back in the form of a triangular ladle in an open mill. The fluororubber compound provided by the invention has low-temperature performance and oil resistance, and can be used for common products and also can be used for fluororubber coatings cured at different temperatures.
Description
Technical Field
The invention relates to the technical field of fluororubber, in particular to fluororubber compound and a preparation method and application thereof; the fluororubber compound provided by the invention has low-temperature performance and oil resistance, and can be used for common products and also can be used for fluororubber coatings cured at different temperatures.
Background
Vinylidene fluoride-hexafluoropropylene (VDF-HFP), vinylidene fluoride-chlorotrifluoroethylene (VDF-CTFE), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene (VDF-HFP-TFE), Tetrafluoroethylene (TFE) -perfluoro (alkyl vinyl ether), or a fluorine-containing elastomer with an active monomer (containing bromine or the like) of the above-mentioned kind has been used as a circular ring, a gasket, a hose, a stem seal, a shaft seal, or the like used under some severe environmental media, because they exhibit excellent chemical resistance, solvent resistance, and heat resistance. In the past decades, the use of fluororubbers has expanded to many new fields, and since the requirements for high temperature and corrosion resistance are more severe, it is necessary to provide materials with excellent properties, thereby expanding the application of some new materials. These requirements not only include general rubber articles, but also relate to some applications of interest, including coatings. Unfortunately, in the field of rubber articles, coating technology has not attracted sufficient attention. Conventional rubber processes often do not take into account differences in the handling and application of coatings, which do not present any significant problems for many elastomer systems, which can be important for fluororubbers to ensure a compact appearance. In recent years, coating materials made of fluororubber have excellent properties and are more satisfactory for use under severe conditions than general rubber coatings. For example, it can be used in supersonic aircraft (fast flight speed, high temperature), in chemical plants, oil refineries, oil well drilling platforms, etc. It can also be used for storage tanks, pipelines, pumps and valves, fans, exhaust pipelines, chimneys, tables, floors, walls, etc. which have strong corrosiveness and certain temperature. It can also be used for protective layer of various rubbers and plastics and coating of various fibers, woven fabrics and glass cloth.
The fluororubber paint has the advantages of convenient use, and the well-known plastic king-polytetrafluoroethylene is a high polymer containing fluorine atoms, has excellent acid and alkali resistance and various medium resistance, but is difficult to process and expensive. The fluorine-containing resin is used for preparing the coating, so that the corrosion resistance is good, but the construction process is difficult, and the coating can be formed only by baking at a high temperature of about 400 ℃, so that the use of the coating is limited. With the development and application of fluororubbers, fluororubber coatings have been developed. Like common paint, the fluororubber paint can be sprayed or brushed, if a proper curing system is selected, a paint film can be cured at room temperature, so that the fluororubber paint can be used on large-scale members and equipment, and is convenient to use, and therefore, the development of the fluororubber paint to meet the requirements of novel industries is extremely necessary.
CN102504448A discloses a low-temperature-resistant and novel-fuel-resistant low-pressure-change fluororubber compound and a preparation method thereof, wherein the fluororubber compound comprises the following components in percentage by weight: 65-75% of fluororubber premixed glue, 3-6% of an acid acceptor, 10-20% of a filler, 10-12% of a pigment and 1-2% of a lubricant, wherein the fluororubber premixed glue is ternary fluororubber premixed glue with a fluorine content of 68% and a bisphenol vulcanization system, the filler is wollastonite, and the pigment is chromium oxide green; the lubricant is plant extracted wax, and the acid absorbent is magnesium oxide MA-150 and calcium hydroxide NICC 5000; the rubber compound is resistant to low temperature and low pressure change, resistant to FAMB methanol gasoline and biodiesel (RME), good in vulcanization process, green, environment-friendly, low in cost and good in storage safety. However, the above low temperature mainly means low temperature brittleness-35 ℃, and the above patent document only specifies the formation of the article and does not mention the use for lower temperature and other uses.
CN108641240A discloses a low-temperature-resistant rubber material for oil seal, which is composed of the following raw materials in parts by weight: 56-80 parts of modified fluororubber, 12-20 parts of filler, 8-15 parts of coumarone resin, 1-9 parts of polyphenylene sulfide, 0.1-0.5 part of hydroxyethyl cellulose, 5-11 parts of alum powder, 0.3-0.9 part of dimethyl silicone oil, 2-7 parts of anti-aging agent and 4-9 parts of sulfur; the rubber material for the low-temperature-resistant oil seal has good low-temperature resistance, oil resistance, mechanical property and vibration reduction performance. However, the rubber material is only modified physically, i.e., modified from the molecular structure in the synthesis of the raw rubber process; the vulcanizing agent adopts sulfur, and the sulfur has certain danger in the vulcanization of the fluororubber in the prior application and is gradually eliminated; furthermore, the low temperature resistance mentioned in the above patent documents is only-25 ℃, and the resistance to lower temperatures is not mentioned; its use is also limited to oil seal compounds only, and no further use is mentioned.
CN111234428A discloses a low temperature resistant and solvent resistant fluororubber heat shrinkable tube and a preparation method thereof, wherein the formula comprises the following components by weight: 80-100 parts of fluoroelastomer, 50-70 parts of fluororesin, 15-35 parts of reinforcing filler, 2-5 parts of acid acceptor and 1-5 parts of plasticizer; the fluororubber heat-shrinkable tube can meet the low-temperature impact at the temperature of-40 ℃, has good solvent resistance and can be used as a heat-shrinkable tube. However, the above-mentioned fluororubber heat shrinkable tube can satisfy low temperature impact and solvent resistance, but oil resistance and other uses are not mentioned.
CN102617956A discloses a high and low temperature resistant and oil resistant ternary blend material of fluororubber, silicone rubber and fluorosilicone rubber and a preparation method thereof, wherein three polymers of peroxide vulcanized fluororubber, methyl vinyl silicone rubber and fluorosilicone rubber are blended to prepare the high and low temperature resistant and oil resistant material; the composition of the rubber comprises the following components: 50-60%, silicone rubber: 20-30%, fluorosilicone rubber, 5-10%, white carbon black: 5-8%, nano kaolin: 8% of peroxide curing agent DCP: 1%, crosslinking assistant TAIC: 1 percent; the vulcanized rubber has a wider use temperature range, can be used for a long time at the temperature of minus 45 ℃ to 250 ℃, and has good oil resistance. However, in the above patent document, three kinds of rubbers are used as a mixed rubber material, and the compatibility between silicone rubber and fluororubber is very poor, so that the above method is difficult to be applied and popularized in actual production; in addition, the effect of the added silicon rubber in a special oil medium is poorer; moreover, the mixed rubber material is mainly used for manufacturing vulcanized products, and no more purposes are mentioned.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a fluororubber mixed rubber and a preparation method and application thereof.
As a first object of the present invention, there is provided a fluororubber compound; the fluororubber gross rubber has good physical and mechanical properties, and also has good low-temperature performance and oil resistance.
Specifically, the fluororubber compound is prepared from the following raw materials in parts by weight:
100 portions of fluororubber modified crude rubber
1.7-4.7 parts of vulcanization assistant
10-40 parts of modified diatomite filler;
wherein the modified diatomite filler is: and (2) carrying out surface treatment on the diatomite by using a fluorine-containing surfactant, wherein the fluorine-containing surfactant accounts for 1-5% of the diatomite.
The invention unexpectedly discovers that the mechanical property of the rubber material is further improved by using the fluororubber modified crude rubber, the vulcanization auxiliary agent and the modified diatomite filler in a combined manner, and the low-temperature property and the oil resistance of the rubber material are improved, so that the rubber material can be used in a more precise and harsh environment.
In the technical scheme, the preparation method of the modified diatomite filler comprises the following steps: weighing granular diatomite raw materials, adding 1-5% of fluorine-containing surfactant into a closed container, mixing for 4 hours, and then storing in the closed container for 8-12 hours (preferably 10 hours). The modified diatomite filler is adopted to replace the diatomite filler, so that the low-temperature resistance of the rubber material can be improved, and the modified diatomite filler is matched with other raw materials in the formula for use, so that the oil resistance of the rubber material can be improved under the low-temperature condition, and the cost is reduced.
In order to further improve the performance of the fluororubber compound, the invention preferably selects the components in the raw materials, and specifically comprises the following steps:
preferably, the molecular weight of the fluororubber modified raw rubber is 5.0-10.0 ten thousand, and the Mooney viscosity is 20-40 MU.
Preferably, the raw rubber modified by the fluororubber is selected from one or more of vinylidene fluoride-hexafluoropropylene (VDF-HFP), vinylidene fluoride-hexafluoropropylene (VDF-HFP) -csm, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-csm; preferably vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-csm;
wherein "csm" represents the cure site monomer;
further, the vulcanization point monomer is a vinylidene fluoride ether monomer.
In a specific embodiment, the fluororubber modified raw rubber can adopt a grade of Chenguang CGFT300-20LT, which is available from Zhonghao Chenguang chemical research institute Co; the product is ternary modified crude rubber, and the molecular weight of the product is 5.0-10.0 ten thousand.
Preferably, the vulcanizing assistant is one or more selected from bisphenol AF, BPP, DCP, bis 2.5, amine vulcanizing agent and TAIC; preferably a mixture of an amine vulcanizing agent, bisphenol AF and BPP.
In the invention, the fluororubber raw rubber modified by the ternary vulcanization point-containing monomer at low Mooney is used as a main base material, wherein the fluororubber raw rubber can be vulcanized in a mixed vulcanization system although the vulcanization point monomer is added, and the crosslinking degree is excellent; meanwhile, the raw material formula adopts a mode of combining an amine and polyol vulcanization system, and the fluororubber modified raw rubber and the modified diatomite filler are matched for mixing to prepare the fluororubber rubber compound with excellent performance.
In the raw material formula, the fluororubber modified raw rubber, the vulcanization auxiliary agent and the modified diatomite filler are cooperatively matched and jointly play a role, so that the physical and mechanical properties of the rubber can be improved, and the low-temperature performance and the oil resistance (such as media such as aviation-resistant kerosene) of the rubber can be improved.
Preferably, the raw materials of the fluororubber compound also comprise 10-40 parts by weight of reinforcing white filler;
the reinforcing white filler is selected from one or more of barium sulfate, calcium silicate, calcium carbonate and kaolin.
Preferably, the raw materials of the fluororubber compound further comprise 4-12 parts by weight of an acid acceptor and 0.1-1 part by weight of a release agent;
preferably, the acid absorbent is selected from one or more of light magnesium oxide, neutral magnesium oxide, high-activity magnesium oxide, calcium oxide and calcium hydroxide; the acid scavenger is commercially available product, and can be exemplified by magnesium oxide 150 manufactured by Nippon corporation and/or ultrafine calcium hydroxide NICC5000 manufactured by KOCHI corporation;
preferably, the release agent is selected from one or more of organosilicon modified silanes and fluorine waxes; the release agents are all common commercial products, for example Struktol WS280 and/or German Ryun A54 can be used.
As a better technical scheme of the invention, the fluororubber compound is prepared from the following raw materials in parts by weight:
according to the invention, the fluorine-containing surfactant (perfluoropolyether oil surfactant) which is autonomously produced by Hao morning light is selected to carry out surface treatment on the diatomite to obtain the modified diatomite filler, so that the surface of the additive can contain fluorine elements, the intermiscibility with fluororubber is increased, particularly, the adhesive force can be further increased when the modified diatomite filler is made into a coating product, and the performance of special oil media such as aviation-resistant kerosene of a sizing material is improved; meanwhile, under the addition of the vulcanization auxiliary agent, the vulcanization performance and the hot tearing performance of the rubber material are enhanced, so that the vulcanization is promoted to be improved, the flexibility is enhanced, and the low-temperature performance of the rubber material is reduced. In conclusion, the low-temperature-resistant and oil-resistant fluororubber compound can be prepared by selecting and compounding raw materials, and can be popularized and applied in the automobile, aviation and electronic industries.
The invention also provides a preparation method of the fluororubber compound, which comprises the following steps:
(1) mixing an acid absorbing agent, a release agent and a reinforcing white filler to obtain a mixed auxiliary agent;
(2) shearing and mixing a vulcanization aid and fluororubber modified raw rubber in an open mixing state, and then banburying;
(3) adding the mixing auxiliary agent obtained in the step (1) and the modified diatomite filler into the banburying raw rubber, and then refining;
(4) the thin film is passed back in the form of a triangular ladle in an open mill.
Preferably, the banburying time is 1-2 min/10kg, the temperature is not more than 60 ℃, and the rotating speed is 30-40 r/min;
preferably, the refining time is 3-5 min/10kg, the temperature is 75-80 ℃, and the rotating speed is 36-38 r/min;
preferably, the temperature of the back refining is not more than 50 ℃, and the times are 8-12.
The physical performance parameters of the fluororubber compound prepared by mixing the method are as follows: under the condition of 65HA Shore, the tensile strength is 12MPa, the elongation at break is 300 percent, TR10-40 ℃ and the RP-3 resistant aviation kerosene mass change rate can be less than 20 percent, the requirement of use at-40-250 ℃ can be met, the medium resistance is excellent, and the applicability of high-temperature vulcanized products and medium-low temperature vulcanized fluorine-containing coatings can be met.
The invention also provides application of the fluororubber gross rubber in high-temperature vulcanized products and middle and low-temperature vulcanized fluorine-containing coatings.
The excellent effects of the present invention:
(1) the fluororubber compound provided by the invention has low-temperature performance, can tolerate the temperature of-40 ℃, and simultaneously has oil resistance (endurance to special oil media such as aviation kerosene and hydraulic oil); in addition, the rubber compound has excellent physical properties, can be used as a high-temperature vulcanized product of a fluorine rubber compound, can be vulcanized at a medium and low temperature to prepare a fluorine-containing coating, and meets the application requirements of multiple purposes.
(2) According to the invention, the fluororubber gross rubber, the vulcanization auxiliary agent, the modified diatomite filler and other auxiliary agents are selected and mixed in proportion, and the fluororubber rubber compound prepared by adopting a special mixing method and a vulcanization process is adopted, so that the physical and mechanical properties of the rubber material are ensured, the low-temperature property and the oil resistance of the rubber material are improved, and the application of the fluororubber gross rubber as a high-temperature vulcanized product and a medium-low temperature vulcanized fluorine-containing coating is met.
(3) The fluororubber compound is suitable for sundry products in industries such as automobiles, aerospace, chemical machinery and the like and hot-pressing buffer materials in the electronic industry, improves the elastic deformation of the rubber material during hot pressing and excellent mechanical and processing properties, and compared with foreign high-price materials, the multifunctional and improved rubber material can resist the monopoly situation of foreign rubber on one hand, promotes the application and popularization of the foreign special formula rubber material on the other hand, and lays a corresponding foundation for replacing the foreign rubber.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The fluororubber modified crude rubber CGFT300-20LT referred to in the examples is purchased from Hao Chen photochemical research institute Co., Ltd; the No. 3 vulcanizing agent is purchased from Gongtianlong science and technology GmbH; bisphenol AF and BPP are both available from Holrewell, Germany; magnesium oxide 150 was purchased from japan; ultra-fine calcium hydroxide NICC5000 was purchased from KOCHI, Japan; WS280 was purchased from Struktol; a54 was purchased from Rhein, Germany.
Example 1
The embodiment provides a fluororubber compound prepared from the following components:
the preparation method of the modified diatomite filler comprises the following steps: weighing granular diatomite raw materials, adding 1-5% of fluorine-containing surfactant into a closed container, mixing for 4 hours, and then storing in the closed container for 10 hours.
The preparation method of the fluororubber compound comprises the following steps:
(1) preparing 150 parts of magnesium oxide, 500 parts of ultrafine calcium hydroxide (NICC), 280 parts of WS, A54 parts of ultrafine calcium hydroxide and barium sulfate according to the proportion of a formula, wherein the amount of the raw rubber is 10kg per car, and hermetically mixing the raw rubber and the ultrafine calcium hydroxide in a container to prevent the auxiliary agent from losing efficacy;
(2) shearing and mixing a 3# vulcanizing agent, bisphenol AF, BPP and CGFT300-20LT in an open mixing state to uniformly mix the four materials together to form a premixed rubber containing the vulcanizing agent, standing, and hermetically storing; adding the pre-mixing rubber into a pressurized internal mixer, wherein the internal mixing time is 1-2 min/10kg, the internal mixing temperature is not more than 60 ℃, and the internal mixing speed is controlled at 36 r/min;
(3) adding the mixing auxiliary agent obtained in the step (1) and the modified diatomite filler into an internal mixer for refining; refining time is 3-5 min/10kg at intervals, banburying temperature is 75-80 ℃, and banburying rotating speed is controlled at 36-38 r/min; placing for 24 hours after banburying is finished;
(4) back refining in a triangular ladle mode in an open mill; the temperature of the back refining is not more than 50 ℃, and the back refining is carried out for 10 times;
(5) and (6) sheet discharging, detection and packaging.
Example 2
The embodiment provides a fluororubber compound prepared from the following components:
the preparation method of the modified diatomaceous earth filler and the preparation method of the fluororubber compound were the same as in example 1.
Example 3
The embodiment provides a fluororubber compound prepared from the following components:
the preparation method of the modified diatomaceous earth filler and the preparation method of the fluororubber compound were the same as in example 1.
Example 4
The embodiment provides a fluororubber compound prepared from the following components:
the preparation method of the modified diatomaceous earth filler and the preparation method of the fluororubber compound were the same as in example 1.
Comparative example 1
The comparative example provides a fluororubber compound prepared from the following components:
the common raw ternary rubber is a ternary copolymer FKM246 of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene;
the preparation method of the fluororubber compound was the same as in example 1.
Test example 1 physical and chemical Properties of fluororubber Compound
In the test example, the physical and chemical properties of the fluororubber rubber compounds prepared in the examples 1 to 4 and the comparative example 1 are detected by a national standard method, and the results are shown in table 1:
TABLE 1 physicochemical Properties of fluororubber mixes obtained in examples 1 to 4 and comparative example 1
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. The fluororubber compound is characterized by being prepared from the following raw materials in parts by weight:
100 portions of fluororubber modified crude rubber
1.7-4.7 parts of vulcanization assistant
10-40 parts of modified diatomite filler;
wherein the modified diatomite filler is: and (2) carrying out surface treatment on the diatomite by using a fluorine-containing surfactant, wherein the fluorine-containing surfactant accounts for 1-5% of the diatomite.
2. A fluororubber blend according to claim 1, wherein the fluororubber-modified raw rubber has a molecular weight of 5.0 to 10.0 ten thousand and a Mooney viscosity of 20 to 40 MU.
3. A fluororubber blend according to claim 1 or 2, wherein said fluororubber-modified raw rubber is selected from one or more of vinylidene fluoride-hexafluoropropylene, vinylidene fluoride-hexafluoropropylene-csm, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-csm; preferably vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene-csm.
4. A fluoroelastomer compound according to claim 1, wherein said vulcanization aids are selected from one or more of bisphenol AF, BPP, DCP, bis 2.5, amine vulcanizing agents, TAIC; preferably a mixture of an amine vulcanizing agent, bisphenol AF and BPP.
5. A fluororubber compound according to any one of claims 1 to 4, characterized in that the raw materials further comprise 10 to 40 parts by weight of a reinforcing white filler;
the reinforcing white filler is selected from one or more of barium sulfate, calcium silicate, calcium carbonate and kaolin.
6. A fluororubber mixture according to any one of claims 1 to 5, characterized in that the raw materials further comprise 4 to 12 parts by weight of an acid acceptor and 0.1 to 1 part by weight of a release agent;
preferably, the acid absorbent is selected from one or more of light magnesium oxide, neutral magnesium oxide, high-activity magnesium oxide, calcium oxide and calcium hydroxide; and/or the release agent is selected from one or more of organosilicon modified silanes and fluorine waxes.
7. The fluororubber compound according to claim 1, characterized by being prepared from the following raw materials in parts by weight:
8. a method for producing a fluororubber compound according to any one of claims 1 to 7, characterized by comprising:
(1) mixing an acid absorbing agent, a release agent and a reinforcing white filler to obtain a mixed auxiliary agent;
(2) shearing and mixing a vulcanization aid and fluororubber modified raw rubber in an open mixing state, and then banburying;
(3) adding the mixing auxiliary agent obtained in the step (1) and the modified diatomite filler into the banburying raw rubber, and then refining;
(4) the thin film is passed back in the form of a triangular ladle in an open mill.
9. The preparation method according to claim 8, wherein the banburying is carried out for 1-2 min/10kg at a temperature not exceeding 60 ℃ and at a rotation speed of 30-40 r/min;
and/or the refining time is 3-5 min/10kg, the temperature is 75-80 ℃, and the rotating speed is 36-38 r/min;
and/or the temperature of the back refining thin pass is not more than 50 ℃, and the times are 8-12.
10. Use of the fluororubber blend according to any one of claims 1 to 7 in high-temperature vulcanized products and medium-and low-temperature vulcanized fluorine-containing coatings.
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| CN115181379A (en) * | 2022-07-20 | 2022-10-14 | 四达氟塑股份有限公司 | Processing technology of fluororubber sealing ring |
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| CN103772859A (en) * | 2014-01-24 | 2014-05-07 | 中昊晨光化工研究院有限公司 | Modified fluororubber rubber compound and preparation method thereof |
| CN110835446A (en) * | 2018-08-15 | 2020-02-25 | 中昊晨光化工研究院有限公司 | Low-temperature flexible high-wear-resistance fluororubber compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772859A (en) * | 2014-01-24 | 2014-05-07 | 中昊晨光化工研究院有限公司 | Modified fluororubber rubber compound and preparation method thereof |
| CN110835446A (en) * | 2018-08-15 | 2020-02-25 | 中昊晨光化工研究院有限公司 | Low-temperature flexible high-wear-resistance fluororubber compound and preparation method thereof |
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| CN115181379A (en) * | 2022-07-20 | 2022-10-14 | 四达氟塑股份有限公司 | Processing technology of fluororubber sealing ring |
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