CN118109007A - Ultra-high temperature resistant elastomer and preparation method thereof - Google Patents
Ultra-high temperature resistant elastomer and preparation method thereof Download PDFInfo
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- CN118109007A CN118109007A CN202211511646.7A CN202211511646A CN118109007A CN 118109007 A CN118109007 A CN 118109007A CN 202211511646 A CN202211511646 A CN 202211511646A CN 118109007 A CN118109007 A CN 118109007A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 180
- 239000000806 elastomer Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 238000010074 rubber mixing Methods 0.000 claims abstract description 48
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 28
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000007906 compression Methods 0.000 claims abstract description 25
- 230000006835 compression Effects 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 18
- 238000004073 vulcanization Methods 0.000 claims description 68
- 239000010702 perfluoropolyether Substances 0.000 claims description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 238000000465 moulding Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 26
- 230000003712 anti-aging effect Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000006229 carbon black Substances 0.000 claims description 20
- 239000000395 magnesium oxide Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 17
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 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 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 4
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000004636 vulcanized rubber Substances 0.000 abstract description 10
- 239000012752 auxiliary agent Substances 0.000 abstract description 8
- 239000000945 filler Substances 0.000 abstract description 4
- 239000004014 plasticizer Substances 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000013016 damping Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 229920006169 Perfluoroelastomer Polymers 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001973 fluoroelastomer Polymers 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008961 swelling Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/002—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of an ultra-high temperature resistant elastomer. Firstly, adding perfluoroether rubber, an auxiliary agent, a filler and a high-temperature-resistant plasticizer according to a certain mass ratio in an open rubber mixing mill, adjusting processing conditions, and taking out a section of rubber sheet. And then adding the rubber compound sheet and other auxiliary agents into an internal rubber mixer, and mixing for a certain time under certain processing conditions to obtain a second-stage rubber compound. And then the two-stage rubber compound is put into an open rubber mixing mill to be discharged, so that the two-stage rubber compound is obtained. And finally, vulcanizing and forming the two-section rubber sheet according to a certain condition, taking out and placing for a certain time, and preparing an elastomer vulcanized sample. The test result shows that the temperature resistance grade of the vulcanized rubber product reaches more than 300 ℃, the mechanical property and compression set at 300 ℃ are basically the same as those at normal temperature, and the vulcanized rubber product can keep good sealing and damping properties at 300 ℃.
Description
Technical Field
The invention relates to a preparation method of an ultra-high temperature resistant elastomer, belongs to the technical field of modification of a high polymer material formula, and particularly relates to a preparation method of an ultra-high temperature resistant elastomer and application of the ultra-high temperature resistant elastomer in the high temperature resistant field.
Background
The elastomer material is in a rubber state in a use temperature range, so that the elastomer material is widely applied to the field of sealing and shock absorption. Along with the increasingly severe use environment of the elastomer product, the high temperature resistant requirement of the elastomer product is gradually improved, and the prior fluororubber and the derivative product thereof are not suitable for the extreme use environment of the sealing shock absorption of the elastomer. The temperature resistance grade of the existing fluororubber products can only reach 250 ℃ at most, and the ultra-high temperature resistant elastomer products with the temperature resistance grade exceeding 250 ℃ are less in the market. According to the invention, the perfluoro ether rubber, the auxiliary agent, the filler and the ultra-high temperature resistant plasticizer are mixed, the cross-linking auxiliary agent is mixed at low temperature in an internal mixer, and the pressure, the temperature and the time are controlled in a program, so that the ultra-high temperature resistant elastomer product with the temperature resistant grade reaching 300 ℃ is finally obtained. The invention solves the problems of the prior art and materials, and the preparation method is not found in patent reports.
Disclosure of Invention
In order to solve the problems existing in the prior art, the invention provides a preparation method of an ultra-high temperature resistant elastomer.
The following describes a preparation method of the ultra-high temperature resistant elastomer, which comprises the following steps and conditions:
In the invention, the perfluoroether rubber, the auxiliary agent, the filler and the high-temperature resistant plasticizer are mixed by an open rubber mixing mill to prepare a section of mixed rubber sheet. And adding the rubber compound sheet and other auxiliary agents into an internal rubber mixer for mixing to prepare a second-stage rubber compound, and discharging the second-stage rubber compound by an open mill to obtain the second-stage rubber compound sheet. Finally, in a flat vulcanizing machine, vulcanizing and forming the two-section rubber sheet according to a fixed program, taking out and placing for a certain time, and preparing an elastomer vulcanization sample. Compared with the traditional product, the elastomer of the invention can obviously improve the high temperature resistant grade, the high temperature resistant grade can reach more than 300 ℃, and the product of the invention can be used for a long time at 300 ℃.
The open type machine used in the invention is not limited by model and condition parameters, the roll gap adjustment range is 0.1-20 mm, the roll temperature adjustment range is 10-200 ℃, a double-motor variable frequency speed change system is adopted, the roll speed is 0-80 r/min, and the front-back roll speed ratio can be 1:2, adjusting in a range;
The type and condition parameters of the internal mixer used in the invention are not limited, the temperature adjustment range is 25-200 ℃, and the rotor rotating speed is 20-120 rpm;
the perfluoro ether rubber adopted by the invention is a terpolymer of perfluoro (methyl vinyl) ether, tetrafluoroethylene and perfluoro vinyl ether, and the specific parameters are shown in Table 2;
The white carbon black adopted by the invention is one or more of gas phase A200, gas phase A380, gas phase R972, gas phase N20, gas phase R202, sediment Z175, sediment DL-600, sediment DL-808 and sediment VN 3. Preference is given to gas phase A200, precipitate Z175, precipitate DL-600 and precipitate VN3;
the carbon black used in the present invention is one or more of N330, N550, N660, N774, N220 and N339. Preferably N330, N550, N660 and N774;
The perfluoro polyether oil adopted by the invention is perfluoro vinyl ether low molecular weight polymer, PEPE for short, has good compatibility with perfluoro ether rubber, and specific parameters are shown in Table 2;
the accelerator used in the present invention includes one or more of triallyl isocyanurate (accelerator TAIC), N' -m-phenylene bismaleimide (accelerator HVA 2), trimethylolpropane trimethacrylate (accelerator TMPTMA). Preferably accelerator TAIC, accelerator HVA2 and accelerator TMPTMA;
The crosslinking agent used in the present invention includes one or more of dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (bis 2-5), t-butylcumyl peroxide (TBCP) or di-t-butyl peroxide (DTBP). DCP and bis 2-5 are preferred;
The anti-aging agent adopted by the invention comprises one or more of N-phenyl-beta-naphthylamine (anti-aging agent D), 2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent RD), 2-mercaptobenzimidazole (anti-aging agent MB), N-di-N-butyldithiocarbamate (anti-aging agent NBC) and N-isopropyl-N' -phenyl-p-phenylenediamine (anti-aging agent 4010 NA). Preferably an antioxidant RD, an antioxidant MB and an antioxidant 4010NA;
The perfluoroether rubber described in step (a) is a terpolymer of perfluoro (methyl vinyl) ether, tetrafluoroethylene and perfluorovinyl ether. The perfluoro ether rubber has the special thermal stability and chemical stability of fluorine materials, the long-term working temperature is typically-39-288 ℃, the short-term working temperature can reach 315 ℃, and the perfluoro ether rubber still has certain plasticity below the embrittlement temperature, is hard but not brittle and can be bent. All chemicals were stable except for swelling in fluorinated solvents. According to the invention, the perfluoropolyether is added into the formula system to improve the temperature resistance grade of the whole vulcanized rubber, so that the temperature resistance grade of the product exceeds 300 ℃.
The perfluoropolyether in the step (a) is PFPE for short, is a high molecular polymer and is mainly used for high-grade lubricating oil, vacuum pump oil, heat transfer fluid and the like. Depending on the monomers polymerized, perfluoropolyethers generally fall into four different structures: hexafluoropropylene oxide, hexafluoroethylene photooxidation, tetrafluoroethylene photooxidation, and tetrafluorooxetane polymerization followed by fluorination. The perfluoropolyether structure used in the invention is hexafluoropropylene oxide, and the main reason is that the polymer structure of the material has a structure which is not photo-oxidized or fluorinated no matter the other structures are photo-oxidized or fluorinated, so that the integral temperature resistance level of the PFPE is affected;
The white carbon black, the magnesium oxide and the zinc oxide adopted by the invention are all commercial products, and specific manufacturers and parameters are shown in table 1.
TABLE 1 auxiliary agent information Table
The polymers used in the present invention include perfluoroether rubber and perfluoropolyether oil, and specific index parameters are shown in Table 2.
TABLE 2 Polymer raw materials information Table
The invention is implemented as follows
(A) In an open rubber mixing mill, which is a double-roller type, the prior art double-motor variable speed and variable frequency is common, and the prior art double-motor variable speed and variable frequency are not limited, and the prior art double-motor variable speed and variable frequency are changed into the open rubber mixing mill, wherein the mass ratio of the perfluoroether rubber to the zinc oxide to the magnesium oxide to the white carbon black to the perfluoropolyether (PFPE) is 100:1 to 5:2 to 8: 5-20: 40-80: 5 to 20 (preferably 100:1.5 to 4.0:3 to 7:6 to 15:45 to 75:6 to 15, more preferably 100:1.5 to 3.0:4 to 6:8 to 12:50 to 70:8 to 12); the temperature of the roller of the open rubber mixing mill is 50-80 ℃, the roller spacing between two rollers is 2-5 mm, and the front and rear roller speeds are 1:1 to 1.5, mixing for 20 to 50 minutes, and taking out a mixed film;
(b) Adding the rubber sheet, the accelerator, the cross-linking agent and the anti-aging agent into an internal mixer, wherein the mass ratio of the components is 100: 4-10: 2-10: 1 to 3 (preferably 100:5 to 9:3 to 9:1.5 to 3.0, more preferably 100:6 to 9:4 to 8:1.5 to 2.5); the temperature of the internal mixer is 50-100 ℃ (preferably 55-85 ℃, more preferably 55-75 ℃) and the rotating speed is 40-80 rpm, and after mixing for 10-20 minutes, the second-stage mixed rubber is discharged; putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing between two rolls is 1-3 mm, the roll temperature is 50-80 ℃, and the roll speed is 1:1 to 1.5 (preferably 1:1.1 to 1.5, more preferably 1:1.1 to 1.3), and after 3 to 5 minutes of kneading, the two-stage kneaded film is taken out.
(C) Placing the two-stage rubber sheet under the conditions of 20-25 ℃ and 20-40% of humidity for 10-24 hours, then placing the rubber sheet into a flat vulcanizing machine with the temperature regulation range of 150-400 ℃ and the pressure regulation range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing machine: ① 140-170 ℃ for 8-12 minutes, and the pressure is 5-15 MPa; ② 160-180 ℃ for 3-8 minutes, and the pressure is 10-15 MPa; ③ 190-210 ℃ for 200-260 minutes, the pressure is 10-15 MPa, and the vacuum degree of the mold environment of the press vulcanizer is-0.1-0.3 MPa; ④ 240-260 ℃ for 230-250 minutes, and the pressure is 10-15 MPa, and the vacuum degree of the mold environment of the press vulcanizer is-01 to-0.3 MPa; ⑤ 290-310 deg.c for 110-130 min, pressure of 8-12 MPa, and environment vacuum degree of 0.4-0.8 MPa.
The temperature resistance grade of the vulcanized rubber product reaches above 300 ℃, the mechanical property and compression set at 300 ℃ are basically the same as those at normal temperature, and the vulcanized rubber product can keep good sealing and damping properties at 300 ℃.
The beneficial effects are that:
compared with the prior art, the invention has the following beneficial effects:
(a) The invention can prepare the ultra-high temperature resistant elastomer product used in the environment of 300 ℃ for a long time by mixing the perfluoro ether rubber with the auxiliary agent, the filler and the ultra-high temperature resistant plasticizer, and the detail is shown in table 3.
(B) The rubber product of the invention has small compression set change at 300 ℃ and low mechanical property change, and the detailed result is shown in Table 3.
Detailed Description
Example 1:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR-94), zinc oxide, magnesium oxide, white carbon black gas phase A200, carbon black N330 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:1:2:5:40: 5. Roller temperature of the open rubber mixing mill is 50 ℃, roller spacing is 2mm, and front and rear roller speed is 1:1.5, after mixing for 20 minutes, taking out a section of mixed film;
(b) Adding a section of rubber sheet, an accelerator TAIC, a cross-linking agent DCP and an anti-aging agent RD into an internal rubber mixer, wherein the mass ratio of the components is 100:4:2:1. and (3) mixing for 10 minutes at the temperature of 50 ℃ at the rotating speed of 40 rpm in the internal mixer, and discharging the second-stage mixed rubber. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2 mm, the roll temperature is 50 ℃, and the roll speed is 1:1, after mixing for 3 minutes, taking out a two-stage mixing film;
(c) Placing the two-stage rubber sheet for 10 hours at the temperature of 20 ℃ and the humidity of 40%, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 140 ℃ for 12 minutes under 5MPa; ② 160 ℃ for 8 minutes and 10MPa; ③ 190 ℃ for 260 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.1 MPa; ④ 240 ℃ for 250 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.1 MPa; ⑤ 290 ℃ for 130 minutes, the pressure is 8MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.4 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 20 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 2:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, carbon black N660 and N774 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:2:5:10:40:20: 10. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 3mm, and front and rear roller speeds are 1:1.2, after mixing for 30 minutes, taking out a section of mixed film;
(b) Adding a section of rubber sheet, an accelerator HVA2, double 2-5 and an anti-aging agent 4010NA into an internal rubber mixer, wherein the mass ratio of each component is 100:8:5:2. and (3) discharging the second-stage rubber compound after the temperature of the internal rubber mixer is 60 ℃ and the rotating speed is 60 r/min and the mixing time is 15 minutes. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2 mm, the roll temperature is 70 ℃, and the roll speed is 1:1.2, after mixing for 4 minutes, taking out the two-stage mixing film;
(c) Placing the two-stage rubber sheet under the conditions of the temperature of 23 ℃ and the humidity of 30% for 16 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 150 ℃ for 12 minutes and 10MPa; ② 170 ℃ for 5 minutes and the pressure is 12MPa; ③ 200 ℃ for 240 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ④ 250 ℃ for 240 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ⑤ 300 ℃ multiplied by 120 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.5 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 23 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 3:
(a) In an open rubber mixing mill, perfluoro ether rubber (FFKM-G80X), zinc oxide, magnesium oxide, precipitated DL-600, precipitated VN3, N550, N660, N774 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:5:8:10:10:40:20:20: 20. Roller temperature of the open rubber mixing mill is 80 ℃, roller spacing is 5mm, and front and rear roller speeds are 1:1, after 50 minutes of mixing, taking out a section of mixing film;
(b) Adding a section of mixing film, an accelerator TMPTMA, a accelerator DCP and an antioxidant MB into an internal rubber mixer, wherein the mass ratio of the components is 100:5:10:3. and (3) discharging the second-stage rubber compound after the temperature of the internal rubber mixer is 100 ℃ and the rotating speed is 80 rpm and the mixing time is 20 minutes. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 3mm, the roll temperature is 80 ℃, and the roll speed is 1:1.3, after 5 minutes of mixing, taking out the two-stage mixing film
(C) Placing the two-stage rubber sheet under the conditions of 25 ℃ and 20% of humidity for 24 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 170 ℃ for 8 minutes, and the pressure is 15MPa; ② 180 ℃ for 3 minutes under 15MPa; ③ 210 ℃ for 200 minutes, the pressure is 15MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.3 MPa; ④ 260 ℃ for 230 minutes, the pressure is 15MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.3 MPa; ⑤ 310 ℃ for 110 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the press vulcanizer is-0.5 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 25 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 4:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR-94), zinc oxide, magnesium oxide, white carbon black gas phase A200, carbon black N330, N550, N774 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:1:2:5:20:10:10: 5. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 2mm, and front and rear roller speeds are 1:1.1, after mixing for 40 minutes, taking out a section of mixed film;
(b) Adding a section of rubber sheet, an accelerator HVA2, a cross-linking agent double 2-5 and an anti-aging agent 4010NA into an internal rubber mixer, wherein the mass ratio of each component is 100:4:2:1. and (3) mixing the mixture for 12 minutes at the temperature of 50 ℃ at the rotating speed of 50 rpm in the internal mixer, and discharging the second-stage mixed rubber. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2mm, the roll temperature is 50 ℃, and the roll speed is 1:1.1, after mixing for 4 minutes, taking out a two-stage mixing film;
(c) Placing the two-stage rubber sheet under the conditions of the temperature of 23 ℃ and the humidity of 35% for 12 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 150 ℃ for 10 minutes under 10MPa; ② 170 ℃ for 10 minutes and the pressure is 12MPa; ③ 200 ℃ for 250 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ④ 250 ℃ for 260 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ⑤ 300 ℃ for 140 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.6 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 23 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 5:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, carbon black N330, N550, N774 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:2:5:10:40:10:10: 10. Roller temperature of the open rubber mixing mill is 55 ℃, roller spacing is 2.5 mm, and front and rear roller speed is 1:1.1, after 25 minutes of mixing, taking out a section of mixing film;
(b) Adding a section of rubber sheet, an accelerator TAIC, a cross-linking agent DCP and an anti-aging agent RD into an internal rubber mixer, wherein the mass ratio of the components is 100:7.5:3.5:1. and (3) mixing the mixture for 12 minutes at the temperature of 55 ℃ at the rotating speed of 50 rpm in the internal mixer, and discharging a second-stage mixed compound. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 1.5 mm, the roll temperature is 65 ℃, and the roll speed is 1:1.1, after mixing for 3 minutes, taking out a two-stage mixing film;
(c) Placing the two-stage rubber sheet under the conditions of 25 ℃ and 35% of humidity for 16 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 150 ℃ for 12 minutes and 10MPa; ② 170 ℃ for 5 minutes and 10MPa; ③ 200 ℃ for 240 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ④ 250 ℃ for 240 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ⑤ 300 ℃ multiplied by 120 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.5 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 25 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 6:
(a) In an open rubber mixing mill, perfluoro ether rubber (FFKM-G80X), zinc oxide, magnesium oxide, precipitated DL-600, precipitated VN3, carbon black N330, N550, N660 and perfluoro polyether (PFPE) are mixed according to a mass ratio of 100:5:8:10:10:40:20:20: 20. Roller temperature of the open rubber mixing mill is 70 ℃, roller spacing is 4 mm, and front and rear roller speeds are 1:1.1, after mixing for 40 minutes, taking out a section of mixed film;
(b) Adding a section of rubber sheet, an accelerator TMPTMA, a cross-linking agent double 2-5 and an anti-aging agent MB into an internal rubber mixer, wherein the mass ratio of each component is 100:5:10:3. and (3) discharging the second-stage rubber compound after the temperature of the internal rubber mixer is 90 ℃ and the rotating speed is 70 rpm and the mixing time is 15 minutes. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2.5 mm, the roll temperature is 70 ℃, and the roll speed is 1:1.2, after mixing for 4 minutes, taking out the two-stage mixed film
(C) Placing the two-stage rubber sheet under the conditions of the temperature of 23 ℃ and the humidity of 30% for 18 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 170 ℃ for 6 minutes and the pressure is 12MPa; ② 180 ℃ for 2 minutes at a pressure of 12MPa; ③ 200 ℃ for 200 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ④ 250 ℃ for 230 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the press vulcanizer is-0.2 MPa; ⑤ 300 ℃ multiplied by 110 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.4 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 23 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 7:
(a) In an open rubber mixing mill, perfluoro ether rubber (FFKM-G80X), zinc oxide, magnesium oxide, precipitated VN3, gas phase A200, carbon black N330, N660, N774 and perfluoro polyether (PFPE) are mixed according to the mass ratio of 100:2:5:5:5:20:20:20: 15. Roller temperature of the open rubber mixing mill is 50 ℃, roller spacing is 2mm, and front and rear roller speed is 1:1.1, after 25 minutes of mixing, taking out a section of mixing film;
(b) Adding a section of rubber sheet, an accelerator TAIC, double 2-5 and an anti-aging agent RD into an internal rubber mixer, wherein the mass ratio of each component is 100:7:6:1. and (3) mixing for 20 minutes at the temperature of 50 ℃ at the rotating speed of 40 rpm in the internal mixer, and discharging the second-stage mixed rubber. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 1.5 mm, the roll temperature is 60 ℃, and the roll speed is 1:1.1, after mixing for 3 minutes, taking out a two-stage mixing film;
(c) Placing the two-stage rubber sheet under the conditions of the temperature of 25 ℃ and the humidity of 40% for 16 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 150 ℃ for 10 minutes and the pressure is 12MPa; ② 175 ℃ for 5 minutes and 10MPa; ③ 205 ℃ for 240 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.1 MPa; ④ 255 ℃ for 240 minutes, the pressure is 10MPa, and the vacuum degree of the mold environment of the press vulcanizer is-0.1 MPa; ⑤ 305 ℃ for 120 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.4 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 25 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Example 8:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, white carbon black sediment VN3, carbon black N330, N550, N660, N774 and perfluoro polyether are mixed according to the mass ratio of 100:2:5:10:20:10:20:10: 10. Roller temperature of the open rubber mixing mill is 40 ℃, roller spacing is 1.5 mm, and front and rear roller speed is 1:1.2, after mixing for 30 minutes, taking out a section of mixed film;
(b) Adding a section of rubber sheet, accelerator HVA2, DCP and antioxidant 4010NA into an internal mixer, wherein the mass ratio of each component is 100:8:4:2. and (3) mixing the mixture for 30 minutes at the temperature of 55 ℃ at the rotating speed of 50 rpm in the internal mixer, and discharging a second-stage mixed compound. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2.5 mm, the roll temperature is 50 ℃, and the roll speed is 1:1.2, after mixing for 5 minutes, taking out the two-stage mixing film;
(c) Placing the two-stage rubber sheet under the conditions of 20 ℃ and 30% of humidity for 14 hours, then placing the rubber sheet into a vulcanizing press with the temperature regulation and control range of 150-400 ℃ and the pressure regulation and control range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing press: ① 155 ℃ for 12 minutes at a pressure of 12MPa; ② 170 ℃ for 6 minutes and the pressure is 12MPa; ③ 200 ℃ for 245 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.3 MPa; ④ 250 ℃ for 245 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.3 MPa; ⑤ 300 ℃ multiplied by 125 minutes, the pressure is 12MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.6 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 23 ℃, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 1:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, N660, N774 and perfluoro polyether are mixed according to the mass ratio of 100:2:5:10:40:20: 10. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 3mm, and front and rear roller speeds are 1:1.1, after mixing for 30 minutes, taking out a section of mixed film;
(b) Adding a rubber sheet, an accelerator HVA2, a cross-linking agent double 2-5 and an anti-aging agent 4010NA into an internal rubber mixer, wherein the mass ratio of each component is 100:8:5:2. and (3) discharging the second-stage rubber compound after the temperature of the internal rubber mixer is 60 ℃ and the rotating speed is 60 r/min and the mixing time is 15 minutes. Putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing is 2 mm, the roll temperature is 70 ℃, and the roll speed is 1:1, after mixing for 4 minutes, taking out a two-stage mixing film;
(c) And placing the two-stage mixed film for 16 hours at the temperature of 23+/-2 ℃ and the humidity of 30%, and then putting the two-stage mixed film into a flat vulcanizing machine for vulcanization molding, wherein the vulcanization condition is 150 ℃ multiplied by 30 minutes. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 2:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, carbon black N660 and N774, accelerator HVA2, cross-linking agent double 2-5, anti-aging agent 4010NA and perfluoro polyether are mixed according to the mass ratio of 100:2:5:10:40:20:4.3:2.7:1.1: 10. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 3 mm, and front and rear roller speeds are 1:1.1, after mixing for 30 minutes, taking out a section of mixed film;
(b) Placing a section of mixed rubber sheet for 16 hours at the temperature of 23 ℃ and the humidity of 30%, and then placing the mixed rubber sheet into a flat vulcanizing machine with the temperature control range of 150-400 ℃ and the pressure control range of 5-15 MPa for vulcanization molding, wherein the vulcanizing machine control program is as follows: ① 150 ℃ for 10 minutes under 10MPa; ② 170 ℃ for 5 minutes and the pressure is 12MPa; ③ 200 ℃ for 240 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ④ 250 ℃ for 240 minutes, the pressure is 12MPa, and the vacuum degree of the mold environment of the vulcanizing press is-0.2 MPa; ⑤ 300 ℃ multiplied by 120 minutes, the pressure is 10MPa, and the vacuum degree of the die environment of the press vulcanizer is-0.5 MPa. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 3:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, N660 and N774, accelerator HVA2, cross-linking agent double 2-5, anti-aging agent 4010NA and perfluoro polyether are mixed according to the mass ratio of 100:2:5:10:40:20:4.3:2.7:1.1: 10. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 3 mm, and front and rear roller speeds are 1:1.1, after mixing for 30 minutes, taking out a section of mixed film;
(b) And placing the two-stage mixed film for 16 hours at the temperature of 23 ℃ and the humidity of 30%, and then putting the two-stage mixed film into a flat vulcanizing machine for vulcanization molding, wherein the vulcanization condition is 150 ℃ multiplied by 30 minutes. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 4:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, white carbon black gas phase A200, carbon black N330, an accelerator TAIC, a cross-linking agent DCP, an anti-aging agent RD and perfluoro polyether are mixed according to a mass ratio of 100:1:2:5:40:2.6:1.3:0.7: 5. Roller temperature of the open rubber mixing mill is 50 ℃, roller spacing is 2 mm, and front and rear roller speed is 1:1.1, after mixing for 20 minutes, taking out a section of mixed film;
(b) And placing a section of the mixed film for 10 hours at the temperature of 20 ℃ and the humidity of 40%, and then putting the mixed film into a flat vulcanizing machine for vulcanization molding, wherein the vulcanization condition is 150 ℃ multiplied by 30 minutes. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 5:
(a) In an open rubber mixing mill, perfluoro ether rubber (FFKM-G80X), zinc oxide, magnesium oxide, precipitated DL-600, precipitated VN3, N550, N660, N774, accelerator TMPTMA, cross-linking agent DCP, anti-aging agent MB and perfluoro polyether oil are mixed according to the mass ratio of 100:5:8:10:10:40:20:20:2.1:4.3:1.3: 20. Roller temperature of the open rubber mixing mill is 80 ℃, roller spacing is 5mm, and front and rear roller speeds are 1:1.1, after 50 minutes of mixing, taking out a section of mixing film;
(b) And (3) placing the first section of the mixed film for 24 hours at the temperature of 25 ℃ and the humidity of 20%, and then putting the mixed film into a flat vulcanizing machine for vulcanization molding, wherein the vulcanization condition is 150 ℃ multiplied by 30 minutes. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
Comparative example 6:
(a) In an open rubber mixing mill, perfluoro ether rubber (Tecnoflon FFKM PFR and 94), zinc oxide, magnesium oxide, sediment Z175, N660 and N774, accelerator HVA2, cross-linking agent double 2-5 and anti-aging agent 4010NA are mixed according to the mass ratio of 100:2:5:10:40:20:4.3:2.7:1.1 addition. Roller temperature of the open rubber mixing mill is 60 ℃, roller spacing is 3 mm, and front and rear roller speeds are 1:1.1, after mixing for 30 minutes, taking out a section of mixed film;
(b) And placing the two-stage mixed film for 16 hours at the temperature of 23 ℃ and the humidity of 30%, and then putting the two-stage mixed film into a flat vulcanizing machine for vulcanization molding, wherein the vulcanization condition is 150 ℃ multiplied by 30 minutes. After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to normal temperature, and testing the mechanical property, the high temperature resistance level, the compression set and the aging resistance of the elastomer vulcanization sample.
TABLE 3-1 Properties of ultra-high temperature resistant elastomer
* Tensile strength and elongation at break were measured according to "measurement of tensile stress strain properties of GB/T528-2009 vulcanized rubber or thermoplastic rubber".
* The high temperature resistance grade is measured according to GB/T20028-2005 by applying an Arrhenius chart to calculate the storage life and the highest use temperature of the high polymer material.
TABLE 3-2 Properties of ultra-high temperature resistant elastomer
| Performance of | Compression set,% | Ageing resistance,% |
| Example 1 | 25.6 | 95.2 |
| Comparative example 4 | 35.9 | 73.1 |
| Example 2 | 20.8 | 97.6 |
| Comparative example 1 | 25.7 | 80.2 |
| Comparative example 2 | 30.2 | 75.4 |
| Comparative example 3 | 33.5 | 68.7 |
| Example 3 | 22.4 | 96.5 |
| Comparative example 5 | 37.6 | 70.5 |
| Example 4 | 21.8 | 92.6 |
| Example 5 | 25.3 | 96.1 |
| Example 6 | 21.1 | 98.0 |
| Example 7 | 22.1 | 95.8 |
| Example 8 | 21.2 | 97.5 |
| Comparative example 6 | 35.8 | 58.9 |
* Compression set determination of compression set for vulcanized rubber or thermoplastic rubber according to national Standard "GB/T7759.1-2015 part 1: testing at normal temperature and high temperature. Test conditions: compression 25% at 300 ℃ for 72 hours;
* Ageing resistance: aging conditions (300 ℃ C..times.168 hours) were calculated according to the following formula: aging resistance = [ tensile strength after aging (MPa) ×elongation at break (%) after aging ×100% ] and [ tensile strength before aging (MPa) ×elongation at break (%) before aging ].
The high temperature resistance of a specific elastomer/rubber is usually 180 to 200 ℃, and it is theoretically considered that an elastomer/rubber material having a temperature resistance exceeding 400 ℃ is not exceeded, so that an elastomer rubber having a temperature resistance exceeding 250 ℃ is usually referred to as an ultra-high temperature resistant elastomer.
Examples 1 and 4, examples 2 and 1 and 2 and 3 are respectively performance data of ultra-high temperature resistant elastomers with the same compounding system and different process conditions, and from the data, the ultra-high temperature resistant elastomers prepared by the method have high and low temperature mechanical properties, temperature resistance and ageing resistance superior to those of the ultra-high temperature resistant elastomers prepared by the traditional process, and compression set of the ultra-high temperature resistant elastomers prepared by the method is far lower than those of the ultra-high temperature resistant elastomer vulcanized rubber products prepared by the traditional process, so that the method has obvious advantages in terms of preparation process.
Example 4, example 5, example 6, example 7 and example 8 are expansion data for the first three examples. The data analysis shows that all the ultra-high temperature resistant elastomer vulcanized rubber products prepared by the method are better than the data index of the comparative example no matter the formulas are the same, similar or different. This illustrates the advancement of the process of the present invention, and on the other hand, the novel nature of the present invention is reflected by the fact that other inventions do not report on perfluoropolyethers (PFPEs) in the formulation system, and that the present invention applies to the preparation of ultra-high temperature resistant elastomeric materials.
In addition, comparative example 6 is a formulation and production process of the prior perfluoroether rubber, wherein no perfluoropolyether is present in the formulation system, and no stage temperature-controlled vulcanization is employed in the molding process. From the comparison analysis of comparative example 6 with other examples and comparative examples, the tensile strength, elongation at break, high temperature resistance, ageing resistance and compression set index of the ultra-high temperature resistant elastomer vulcanized rubber prepared by the method of the invention are obviously superior to those of the perfluoro ether rubber product prepared by the prior art. Meanwhile, according to various performance indexes, the mechanical property, ageing resistance and compression set performance of the product are very small in change at 300 ℃, and the temperature resistance level is over 300 ℃, so that the ultra-high temperature resistant elastomer product can be used for a long time at 300 ℃ under the condition of thermal oxygen, which is also the invention.
Claims (6)
1. A preparation method of an ultra-high temperature resistant elastomer is characterized in that,
The preparation method comprises the following steps:
(a) In an open rubber mixing mill, which is a double-roller type, the prior art double-motor variable speed and variable frequency is common, and the prior art double-motor variable speed and variable frequency are not limited, and the prior art double-motor variable speed and variable frequency are changed into the open rubber mixing mill, wherein the mass ratio of the perfluoroether rubber to the zinc oxide to the magnesium oxide to the white carbon black to the perfluoropolyether (PFPE) is 100:1 to 5:2 to 8: 5-20: 40-80: 5 to 20 (preferably 100:1.5 to 4.0:3 to 7:6 to 15:45 to 75:6 to 15, more preferably 100:1.5 to 3.0:4 to 6:8 to 12:50 to 70:8 to 12); the temperature of the roller of the open rubber mixing mill is 50-80 ℃, the roller spacing between two rollers is 2-5 mm, and the front and rear roller speeds are 1:1 to 1.5, mixing for 20 to 50 minutes, and taking out a mixed film;
(b) Adding the rubber sheet, the accelerator, the cross-linking agent and the anti-aging agent into an internal mixer, wherein the mass ratio of the components is 100: 4-10: 2-10: 1 to 3 (preferably 100:5 to 9:3 to 9:1.5 to 3.0, more preferably 100:6 to 9:4 to 8:1.5 to 2.5); the temperature of the internal mixer is 50-100 ℃ (preferably 55-85 ℃, more preferably 55-75 ℃) and the rotating speed is 40-80 rpm, and after mixing for 10-20 minutes, the second-stage mixed rubber is discharged; putting the two-stage rubber compound obtained by the internal mixer into an open rubber mixing mill, wherein the roll spacing between two rolls is 1-3 mm, the roll temperature is 50-80 ℃, and the roll speed is 1:1 to 1.5 (preferably 1:1.1 to 1.5, more preferably 1:1.1 to 1.3), and after 3 to 5 minutes of kneading, the two-stage kneaded film is taken out.
(C) Placing the two-stage rubber sheet under the conditions of 20-25 ℃ and 20-40% of humidity for 10-24 hours, then placing the rubber sheet into a flat vulcanizing machine with the temperature regulation range of 150-400 ℃ and the pressure regulation range of 5-15 MPa and the mold environment vacuum degree of-1.0 to-0.1 MPa for vulcanization molding, and controlling the program of the vulcanizing machine: ① 140-170 ℃ for 8-12 minutes, and the pressure is 5-15 MPa; ② 160-180 ℃ for 3-8 minutes, and the pressure is 10-15 MPa; ③ 190-210 ℃ for 200-260 minutes, the pressure is 10-15 MPa, and the vacuum degree of the mold environment of the press vulcanizer is-0.1-0.3 MPa; ④ 240-260 ℃ for 230-250 minutes, and the pressure is 10-15 MPa, and the vacuum degree of the mold environment of the press vulcanizer is-01 to-0.3 MPa; ⑤ 290-310 deg.c for 110-130 min, pressure of 8-12 MPa, and environment vacuum degree of 0.4-0.8 MPa.
2. The method according to claim 1, wherein,
The white carbon black in the step (a) is one or more of gas phase A200, gas phase A380, gas phase R972, gas phase N20, gas phase R202, sediment Z175, sediment DL-600, sediment DL-808 and sediment VN 3;
The carbon black in step (a) is one or more of N330, N550, N660, N774, N220, and N339.
3. The method according to claim 1, wherein,
The accelerator in step (b) comprises one or more of triallyl isocyanurate (accelerator TAIC), N' -m-phenylene bismaleimide (HVA 2), trimethylolpropane trimethacrylate (TMPTMA);
The crosslinking agent in step (b) comprises one or more of dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane (bis 2-5), t-butylcumyl peroxide (TBCP) or di-t-butyl peroxide (DTBP);
the anti-aging agent in the step (b) comprises one or more of N-phenyl-beta-naphthylamine (anti-aging agent D), 2, 4-trimethyl-1, 2-dihydroquinoline polymer (anti-aging agent RD), 2-mercaptobenzimidazole (anti-aging agent MB), nickel N, N-di-N-butyldithiocarbamate (anti-aging agent NBC) and N-isopropyl-N' -phenyl-p-phenylenediamine (anti-aging agent 4010 NA).
4. The method according to claim 1, wherein,
After vulcanization molding is completed, taking out an elastomer vulcanization sample, cooling to 20-25 ℃, and testing the mechanical property, high temperature resistance level, compression set and ageing resistance of the elastomer vulcanization sample.
5. An ultra-high temperature resistant elastomer material prepared by the method of any one of claims 1 to 4.
6. The ultra-high temperature resistant elastomer material according to claim 5, wherein the product can be used for a long time under the condition of 300 ℃, exceeds the temperature resistant grade of common rubber (80-100 ℃) by more than 200 ℃, exceeds the temperature resistant grade of special high temperature resistant rubber (180-200 ℃) by more than 100 ℃, and is the rubber material with the highest temperature resistant grade in the prior published report.
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