CN114874571B - Fluorine-containing rubber material and preparation method thereof - Google Patents
Fluorine-containing rubber material and preparation method thereof Download PDFInfo
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- CN114874571B CN114874571B CN202210662320.8A CN202210662320A CN114874571B CN 114874571 B CN114874571 B CN 114874571B CN 202210662320 A CN202210662320 A CN 202210662320A CN 114874571 B CN114874571 B CN 114874571B
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 229920001971 elastomer Polymers 0.000 title claims abstract description 62
- 239000005060 rubber Substances 0.000 title claims abstract description 58
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000011737 fluorine Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920001973 fluoroelastomer Polymers 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 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 abstract description 14
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 11
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 7
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 7
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical group [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 4
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 11
- 238000005065 mining Methods 0.000 abstract description 4
- 230000032683 aging Effects 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 8
- 238000004073 vulcanization Methods 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- 239000004636 vulcanized rubber Substances 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007541 indentation hardness test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a fluorine-containing rubber material and a preparation method thereof, belonging to the technical field of rubber materials. The fluorine-containing rubber material comprises the following components in percentage by mass: 64.0 to 68.0 percent of fluororubber, 22.0 to 24.0 percent of filler, 0 to 4.0 percent of plasticizer, 4.0 to 5.0 percent of acid absorber, 0.5 to 1.0 percent of processing aid and 3.8 to 4.7 percent of vulcanizing agent; the acid absorbing agent is obtained by mixing calcium hydroxide and magnesium oxide; the processing aid is obtained by mixing organic silicone and octadecylamine; the vulcanizing agent is obtained by mixing triallyl cyanurate, triallyl isocyanurate and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane. The fluororubber material of the invention has particularly excellent flexural fatigue resistance, extremely high elongation at break and low temperature resistance. The rubber sealing piece has excellent performance in a use environment, and is suitable for manufacturing rubber sealing pieces which are required to be resistant to flex fatigue in the aspects of new energy, mining engineering machinery, automobile manufacturing, energy accumulators and the like.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to a fluorine-containing rubber material and a preparation method thereof.
Background
The sealing elements such as rubber diaphragms used in new energy sources, mining engineering machinery, automobile manufacture, energy accumulators and the like need to do periodic rapid reciprocating motion, and in order to ensure sealing, the rubber materials used are required to be high-temperature resistant, multi-medium resistant, weather-resistant and aging resistant, excellent in reciprocating flexural fatigue resistance, high in strength, high in elongation at break and good in low-temperature performance.
Fluororubber is a synthetic polymer elastomer having fluorine atoms attached to carbon atoms of a main chain or a side chain. The fluorine atom has extremely strong electronegativity and small radius, and the formed carbon-fluorine bond has large energy and small covalent bond radius (which is only half of carbon-carbon bonds), so that fluorine atoms can be closely arranged around carbon atoms, a carbon-carbon main chain is well shielded, and chemical inertness of the C-C bond of the fluorine-containing high polymer elastomer is endowed. Moreover, the bond energy of the fluorinated carbon atoms and other atoms is correspondingly improved, so that the heat resistance and corrosion resistance of the fluorine-containing high polymer elastomer are improved. Meanwhile, the fluorine atoms greatly increase the free rotation energy of the chemical bond of the fluorine-containing compound, so that the rigidity of fluorocarbon elastomer molecules is enhanced, and the flexibility and low temperature resistance are reduced, therefore, the introduction of the fluorine atoms endows fluororubber products with a plurality of excellent performances in use environments: high chemical stability, high temperature resistance, aging resistance, good vacuum performance, small air permeability, good electrical performance and excellent mechanical performance.
Because of the many excellent properties of fluororubber, fluororubber has been used in modern aviation, missile, rocket, space navigation, naval vessel, atomic energy and other industrial fields such as automobiles, shipbuilding, chemistry, petroleum, instruments, machinery and the like.
In the prior art, the fluorine rubber can meet the requirements of high temperature resistance, multiple medium resistance, weather aging resistance, higher strength and lower cold resistance, but has poor flexural dynamic fatigue resistance and is damaged after being flexed for about 1 ten thousands of times; the elongation at break is not high (less than or equal to 300%). Therefore, the preparation of a fluororubber material having particularly excellent flex fatigue resistance and extremely high elongation at break is a problem to be solved at present.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of poor bending fatigue resistance and low elongation at break of the fluororubber material in the prior art.
In order to solve the technical problems, the invention provides a fluorine-containing rubber material and a preparation method thereof.
A first object of the present invention is to provide a fluororubber material comprising, in mass fraction: 64.0 to 68.0 percent of fluororubber, 22.0 to 24.0 percent of filler, 0 to 4.0 percent of plasticizer, 4.0 to 5.0 percent of acid absorber, 0.5 to 1.0 percent of processing aid and 3.8 to 4.7 percent of vulcanizing agent; the acid absorbing agent is obtained by mixing calcium hydroxide and magnesium oxide; the processing aid is obtained by mixing organic silicone and octadecylamine; the vulcanizing agent is obtained by mixing triallyl cyanurate, triallyl isocyanurate and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
In one embodiment of the invention, the fluororubber is a ternary fluororubber having a mooney value of 16-26.
In one embodiment of the invention, the ternary fluororubber is TECNOFLON P457 produced by Solvay, belgium. The invention adopts low-Mooney ternary fluororubber TECNOFLON P457 as a main body material, wherein the main chain of the molecule is a saturated carbon chain, and the carbon atoms of the main chain or the side chain are connected with fluorine atoms. The introduction of fluorine atoms endows the fluororubber product with high temperature resistance, oil resistance, corrosion resistance, ozone resistance and thermo-oxidative aging resistance under the use environment; the relatively low molecular weight or the relatively wide molecular weight distribution is beneficial to processing because of low raw rubber Mooney on one hand and relatively more low molecular parts with good flexibility on the other hand, and is beneficial to improving the flexural fatigue resistance and cold resistance of the material; the introduced third monomer is introduced with a vulcanization active point, and a peroxide vulcanization system can be adopted, so that the side chain grafting proportion is improved, the softness of the rubber is improved, and the flexural fatigue resistance and the cold resistance of the material are improved.
In one embodiment of the invention, the filler is barium sulfate.
In one embodiment of the invention, the barium sulfate is Blanc Fixe Supper F produced by German Sa Ha Liben (SACHTLEBEN). The barium sulfate Blanc Fixe Supper F adopted in the invention is fine powder which is subjected to organic coating treatment, has an average particle size of about 1 mu m and a pH value of about 7, improves the affinity of the barium sulfate and the fluorine rubber, ensures that the barium sulfate can better disperse the fluorine rubber to form a stable dispersion system, obviously improves the elongation at break and the strength at break of the rubber material under the condition of limited hardness, improves the flexibility of the rubber material, improves the flexing fatigue resistance of the material, and simultaneously improves the processing performance.
In one embodiment of the invention, the plasticizer is methyl fluorosilicone oil.
In one embodiment of the invention, the methyl fluorosilicone oil is AFS-L-1011 manufactured by Shenzhen Heng New Material technology Co. The methyl fluorosilicone oil AFS-L-1011 is prepared by polymerizing fluorosilicone monomer and has hydroxyl group at two molecular terminals. Because of the introduction of the trifluoropropyl, the fluororubber has excellent electrical insulation property, high and low temperature resistance, high flash point and low solidifying point, can be used for a long time at the temperature of between 50 ℃ below zero and 250 ℃, has small viscosity-temperature coefficient, high compression ratio, low surface tension, good hydrophobic and moisture-proof properties, presents chemical inertia and physiological inertia, has the reactivity of hydroxyl, and can form a stable mixed system with fluororubber. Therefore, the addition of the methyl fluorosilicone oil AFS-L-1011 improves the elongation at break of the material, improves the flex fatigue resistance and the cold resistance, and improves the processability of the fluororubber.
In one embodiment of the invention, the mass ratio of the calcium hydroxide to the magnesium oxide is 3.5-4.5:2.5-3.5.
In one embodiment of the invention, the calcium hydroxide is NICC5000 produced on the Japanese well (INOAC); the magnesium oxide was Kyowamag 150 produced by japan harmony (KYOWA). The NICC5000 adopted in the invention is specially treated calcium hydroxide, and has the advantages of fine fineness, high purity and strong activity. Kyowamag 150 is superfine magnesia powder with special matter as surface treatment, and has high purity, high activity, high acid absorption, excellent polymerization performance, excellent dispersivity and certain reinforcing performance. The two can be used for fluororubber to greatly improve the mixing processing dispersibility of fluororubber, improve the scorching property of sizing material, and also can be used as an acid acceptor to absorb hydrofluoric acid generated during vulcanization of the fluororubber, so that the fluororubber is fully crosslinked, the heat resistance, fatigue resistance and weather resistance of products are improved, and the pollution of the fluororubber to a die is reduced.
In one embodiment of the invention, the mass ratio of the organosilicone to the octadecylamine is 4.5-5.5:3.5-4.5. The organosilicone is STRUKTOLWS 280 produced by Struktol, germany. Octadecylamine is Armeen 18D manufactured by Akzo, alkesinobell, netherlands. STRUKTOLWS 280-280 is a novel organic silicone processing aid, has good compatibility with rubber, lubricates filler particles, promotes filler to disperse in the rubber, facilitates vulcanization and mold filling, reduces mold pollution caused by spraying, reduces product frosting, has extremely low high-temperature volatile matters, and is particularly suitable for fluororubber. Armeen 18D was used as a mold release agent to facilitate vulcanization and demolding of the article.
In one embodiment of the present invention, the mass ratio of triallyl cyanurate, triallyl isocyanurate and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane is 3.5 to 5.0:2.0-3.5:2.7-3.7.
In one embodiment of the invention, the triallyl cyanurate is Langshen Rhenofit TAC/S, germany; the triallyl isocyanurate is Langsheng Rhenofit TAIC/S in Germany; the 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is French Acomat101XL45。
Rhenofit TAC/S is a mixture of 70% triallyl cyanurate uniformly dispersed in 30% silicon dioxide. Rhenofit TAIC/S is a mixture of 70% triallyl isocyanurate uniformly dispersed in 30% silica.101XL45 is a mixture of 45% of the organic peroxide 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane uniformly dispersed in 55% of calcium carbonate.
Rhenofit TAC/S and Rhenofit TAIC/S main components are used as active auxiliary crosslinking agents for peroxide crosslinking, and the molecules of the main components all contain 3 unsaturated groups, and the action mechanism is as follows: in the presence of free radicals, the reactive co-crosslinking agent polymerizes into a multi-branched polymer; the reactive co-crosslinking agent acts with free radicals on the polymer, polymer branches. The generation of branched chains improves the flexibility of the polymer, namely improves the flexural fatigue resistance and high elongation at break of the polymer. The two are pre-dispersed, which is favorable for transportation, use and even dispersion in fluororubber. However, the two materials have different activities, the proper proportion of the materials is developed for matching, the sizing materials are fully crosslinked, a proper amount of branched chain network structure is provided, and the fluororubber material has good flexibility.
The 101XL45 main component is a vulcanization crosslinking agent, and the action mode is as follows: 1. the peroxide radical is generated by thermal decomposition and directly or indirectly absorbs hydrogen on tertiary carbon atoms in fluoropolymer chains or active points on third monomers, so that free radical active centers are generated in fluoropolymer molecules. 2. The free radical active center in the fluoropolymer forms the fluororubber with a crosslinked structure directly or through an active auxiliary crosslinking agent.
Rhenofit TAC/S, rhenofit TAIC/S and under heating101XL45 is combined to form the vulcanized fluororubber material which has excellent flex fatigue resistance, high elongation at break, proper hardness, higher strength, better heat resistance, oil resistance, corrosion resistance, ozone resistance, thermal oxidative aging resistance and cold resistance.
The second object of the present invention is to provide a process for producing the fluororubber material, comprising the steps of,
S1: the fluororubber, the acid absorber and the processing aid are subjected to pressing hammer mixing and then are lifted for cleaning, then the filler and the plasticizer are added into the mixture to be subjected to pressing hammer mixing and then lifted for cleaning again, then the mixture is subjected to pressing hammer mixing, finally the vulcanizing agent is added into the mixture to be subjected to pressing hammer mixing and then discharged at 120-130 ℃, and a mixed rubber sheet is obtained through rollers, sheet discharging and parking;
S2: mixing the mixed rubber sheet in the step S1 for 30-60S, continuously mixing for 60-120S after bolt extraction, discharging at the temperature of not higher than 110 ℃, and obtaining mixed rubber final rubber through roller and sheet discharging;
S3: and (3) keeping the final rubber compound of the S2 at 165-175 ℃ and 10-18MPa for 5-10min, vulcanizing, and then keeping at 170-190 ℃ for at least 6h to obtain the fluorine-containing rubber material.
In one embodiment of the invention, in S1, the mixing time is 60-120S.
In one embodiment of the present invention, in S1, the time for parking is at least 8 hours, and the mixing film is parked for a certain time, so that each component and the fluororubber can be fully soaked, which is favorable for mixing and uniformly dispersing each component and the fluororubber.
In one embodiment of the invention, in S1 and S2, the mixing time and the mixing temperature are ensured, and the uniform mixing and dispersion of the components, the volatilization of low molecular substances and the safety of processing can be ensured.
In one embodiment of the invention, the method further comprises the step of sealing and packaging the fluorine-containing rubber material, wherein the sealing and packaging can isolate an acid absorbent which is extremely easy to absorb moisture in the rubber compound sheet from the outside, so that the moisture absorption is avoided, the rubber compound is prevented from being vulcanized early, the scorching performance is deteriorated, and the stability of the processing performance and the physical performance of the rubber compound is ensured.
Compared with the prior art, the technical scheme of the invention has the following advantages:
The fluororubber material disclosed by the invention is particularly excellent in flexural fatigue resistance, extremely high in elongation at break and low-temperature resistant. The rubber sealing piece has high temperature resistance, oil resistance, corrosion resistance, ozone resistance, thermal oxidative aging resistance and better cold resistance in the use environment, and is suitable for manufacturing rubber sealing pieces which are required to be resistant to flex fatigue in the aspects of new energy sources, mining engineering machinery, automobile manufacturing, energy accumulators and the like.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
The present invention will be described in detail with reference to examples. The specific cases of the various materials used in the description are shown in table 1:
TABLE 1
Examples
A fluorine-containing rubber material and a preparation method thereof specifically comprise the following steps:
1. The formulations of the fluororubber materials of examples 1 to 4 are shown in Table 2 (in parts by mass):
TABLE 2
2. The preparation of the fluorine-containing rubber material specifically comprises the following steps:
(1) Preparing materials: respectively weighing fluororubber, an acid absorber and a processing aid, and then mixing to form a ingredient A; weighing barium sulfate and methyl fluorosilicone oil to form a mixture B; weighing a special vulcanizing agent to form a mixture C;
(2) First mixing: mixing the components in the ingredients A for 60-120s in an internal mixer, then carrying out hammer lifting cleaning, then adding the ingredients B, carrying out hammer pressing mixing for 60-120s, carrying out hammer lifting cleaning, carrying out hammer pressing mixing for 60-120s, then adding the ingredients C, carrying out hammer pressing mixing for 60-120s, discharging at 125 ℃, discharging after passing through a small roll gap on a material cutting machine for 4 times, and standing for cooling;
(3) Parking the rubber compound: standing the mixed film prepared by the first mixing for 8 hours at room temperature;
(4) And (3) secondary remilling: placing the parked rubber compound into an internal mixer for mixing for 30-60s, continuously mixing for 60-120s after bolt extraction, discharging to a material opening machine at 110 ℃, passing through a roller for 3 times on the open mixer, triangulating for 4 times with small roller spacing, and uniformly discharging to obtain the final rubber compound;
(5) Maintaining the final rubber of the mixed rubber at 170 ℃ and 14MPa for 8min, vulcanizing, and then maintaining for 6h at 180 ℃ to finish secondary vulcanization to obtain a fluorine-containing rubber material;
(6) And (3) packaging: and cooling the fluororubber material to room temperature, and sealing and packaging to complete the preparation.
Wherein the mixing times of examples 1-4 are shown in Table 3:
TABLE 3 Table 3
Comparative example
1. The formulations of the materials of comparative examples 1 to 6 are shown in table 4 (in parts by mass):
TABLE 4 Table 4
2. The preparation of the materials of comparative examples 1-6 specifically included the following steps:
(1) Preparing materials: respectively weighing fluororubber, zinc oxide, an acid absorber and a processing aid, and then mixing to form a mixture A; weighing barium sulfate, sodium aluminum silicate, carbon black, methyl fluorosilicone oil and polyether ester to form a ingredient B; weighing a special vulcanizing agent to form a mixture C;
(2) First mixing: mixing the components in the ingredients A for 60-120s in an internal mixer, then carrying out hammer lifting cleaning, then adding the ingredients B, carrying out hammer pressing mixing for 60-120s, carrying out hammer lifting cleaning, carrying out hammer pressing mixing for 60-120s, then adding the ingredients C, carrying out hammer pressing mixing for 60-120s, discharging at 125 ℃, discharging after passing through a small roll gap on a material cutting machine for 4 times, and standing for cooling;
(3) Parking the rubber compound: standing the mixed film prepared by the first mixing for 8 hours at room temperature;
(4) And (3) secondary remilling: placing the parked rubber compound into an internal mixer for mixing for 30-60s, continuously mixing for 60-120s after bolt extraction, discharging to a material opening machine at 110 ℃, passing through a roller for 3 times on the open mixer, triangulating for 4 times with small roller spacing, and uniformly discharging to obtain the final rubber compound;
(5) Maintaining the final rubber of the mixed rubber at 170 ℃ and 14MPa for 8min, vulcanizing, and then maintaining for 6h at 180 ℃ to finish secondary vulcanization to obtain a fluorine-containing rubber material;
(6) And (3) packaging: and cooling the fluororubber material to room temperature, and sealing and packaging to complete the preparation.
Wherein the mixing times of comparative examples 1 to 6 are shown in Table 5:
TABLE 5
Test case
Physical properties were tested on the materials prepared in examples 1 to 4 and comparative examples 1 to 6.
(1) Hardness: vulcanized rubber or thermoplastic rubber indentation hardness test method, first part: shore durometer (Shore hardness) GB/T531.1-2008.
(2) Tensile strength: measurement of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber GB/T528-2009.
(3) Elongation rate: measurement of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber GB/T528-2009.
(4) 200 ℃ X 72h heat aging: hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber GB/T3512-2014.
(5) Flex cracking: determination of flex cracking and crack growth in vulcanizates or thermoplastic rubbers (model De Mo Xiya) GB/T13934-2006.
(6) Volume change: vulcanized rubber or thermoplastic rubber liquid resistance test method GB/T1690-2010.
(7) Ozone resistance: ozone crack resistant static tensile test for vulcanized rubber or thermoplastic rubber GB/T7762-2014.
(8) Low temperature resistance: measurement of low temperature brittleness of vulcanized rubber Single sample method GB/T1682-2014.
Table 6 shows the relevant parameters for the fluororubber materials of examples 1-4:
TABLE 6
Table 7 shows the relevant parameters for the materials obtained for comparative examples 1-6:
TABLE 7
As can be seen from tables 6 to 7, the rubber materials of examples 1 to 4 of the present invention selected from low Mooney ternary fluororubber TECNOFLON P457 provided matrix materials forming a branched chain and easy to process, 3 materials Rhenofit TAC/S, rhenofit TAIC/S andThe vulcanization system composed of 101XL45 can realize the branching of target materials and the physical properties of design, and the specially treated reinforcing filler and other auxiliary agents can be uniformly dispersed in the main material to fully play respective functions.
The preparation process of the fluororubber material can realize the uniform dispersion of the materials in the rubber main material, and the rubber material structure is converted into a space net structure from linear shape, so that the material has various properties.
Therefore, the rubber materials of the embodiments 1 to 4 of the invention have no cracks after 45 ten thousand times of flexing, and have particularly excellent flexing fatigue; the elongation at break is more than 400%, and the high elongation at break is achieved; the hardness is 60-65ShA, has the characteristics of lower hardness, higher tensile strength, high temperature resistance, oil resistance, corrosion resistance, ozone resistance, thermal-oxidative aging resistance and lower brittleness temperature (-25 ℃), can be used for a long time in a use environment, and is very suitable for manufacturing diaphragms and other rubber sealing elements with similar requirements in the aspects of new energy sources, mining engineering machinery, automobile manufacturing, energy accumulators and the like.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (7)
1. A fluororubber material, characterized by comprising, in mass fraction: 64.0 to 68.0 percent of fluororubber, 22.0 to 24.0 percent of filler, 0 to 4.0 percent of plasticizer, 4.0 to 5.0 percent of acid absorber, 0.5 to 1.0 percent of processing aid and 3.8 to 4.7 percent of vulcanizing agent;
the fluororubber is TECNOFLON P457 produced by Solvay of Belgium;
the filler is barium sulfate; the barium sulfate is Blanc Fixe Supper F produced by Shahali, germany;
the plasticizer is methyl fluorosilicone oil; the methyl fluorosilicone oil is AFS-L-1011 produced by Shenzhen Guanzhen new material technology Co., ltd;
The acid absorbing agent is obtained by mixing calcium hydroxide and magnesium oxide;
The processing aid is obtained by mixing organic silicone and octadecylamine; the organic silicone is STRUKTOLWS and 280 produced by Struktol, germany, and the octadecylamine is Armeen 18D produced by Arkesinobell, netherlands;
The vulcanizing agent is prepared by mixing triallyl cyanurate, triallyl isocyanurate and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane; the triallyl cyanurate is Langsheng Rhenofit TAC/S in Germany, the triallyl isocyanurate is Langsheng Rhenofit TAIC/S in Germany, and the 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is Leperox 101XL45 in Almar in France.
2. The fluororubber material according to claim 1, wherein the mass ratio of calcium hydroxide to magnesium oxide is 3.5-4.5:2.5-3.5.
3. The fluororubber material according to claim 1, wherein the mass ratio of the organosilicone to the octadecylamine is 4.5-5.5:3.5-4.5.
4. The fluororubber material according to claim 1, wherein the mass ratio of triallyl cyanurate, triallyl isocyanurate and 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane is 3.5 to 5.0:2.0-3.5:2.7-3.7.
5. A process for producing a fluororubber material as defined in any one of claims 1 to 4, comprising the steps of,
S1: the fluororubber, the acid absorber and the processing aid are subjected to pressing hammer mixing and then are lifted for cleaning, then the filler and the plasticizer are added into the mixture to be subjected to pressing hammer mixing and then lifted for cleaning again, then the mixture is subjected to pressing hammer mixing, finally the vulcanizing agent is added into the mixture to be subjected to pressing hammer mixing and then discharged at 120-130 ℃, and a mixed rubber sheet is obtained through rollers, sheet discharging and parking;
S2: mixing the mixed rubber sheet in the step S1 for 30-60S, continuously mixing for 60-120S after bolt extraction, discharging at the temperature of not higher than 110 ℃, and obtaining mixed rubber final rubber through roller and sheet discharging;
S3: and (3) keeping the final rubber compound of the S2 at 165-175 ℃ and 10-18MPa for 5-10min, vulcanizing, and then keeping at 170-190 ℃ for at least 6h to obtain the fluorine-containing rubber material.
6. The method for producing a fluororubber material according to claim 5, wherein in S1, the kneading time is 60 to 120 seconds.
7. The method for producing a fluororubber material as claimed in claim 5, wherein in S1, the parking time is at least 8 hours.
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| CN109265878A (en) * | 2018-08-31 | 2019-01-25 | 湖南橡塑密封件厂有限公司 | A kind of excellent warping strength fatigability fluorubber and preparation method thereof of high maximum elongation |
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| CN109265878A (en) * | 2018-08-31 | 2019-01-25 | 湖南橡塑密封件厂有限公司 | A kind of excellent warping strength fatigability fluorubber and preparation method thereof of high maximum elongation |
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