CN115093500A - Preparation method of high-elasticity fluororubber raw rubber - Google Patents
Preparation method of high-elasticity fluororubber raw rubber Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 43
- 229920001971 elastomer Polymers 0.000 title claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 26
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 105
- 239000000178 monomer Substances 0.000 claims description 52
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 51
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 51
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 51
- 239000003999 initiator Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- WZCZNEGTXVXAAS-UHFFFAOYSA-N trifluoromethanol Chemical compound OC(F)(F)F WZCZNEGTXVXAAS-UHFFFAOYSA-N 0.000 claims description 24
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229920006295 polythiol Polymers 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000010702 perfluoropolyether Substances 0.000 claims description 19
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229920001774 Perfluoroether Polymers 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 11
- 230000015271 coagulation Effects 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 11
- GANXFQTZEVGPPI-UHFFFAOYSA-N fluorosulfonyloxyethene Chemical compound FS(=O)(=O)OC=C GANXFQTZEVGPPI-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- -1 1-vinyl-3-butylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- IUAVXIJYHVNRFH-UHFFFAOYSA-N sodium;trifluoromethanolate Chemical compound [Na+].[O-]C(F)(F)F IUAVXIJYHVNRFH-UHFFFAOYSA-N 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 5
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 5
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 238000012824 chemical production Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000007908 nanoemulsion Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 230000008014 freezing Effects 0.000 description 8
- 238000007710 freezing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of chemical production, in particular to a preparation method of high-elasticity fluororubber raw rubber; the preparation method of the high-elasticity fluororubber raw rubber adopts the novel fluorine-containing surfactant to partially replace perfluorooctanoic acid (PFOA), has good stability of a dispersion system, and can be used as a polymerization dispersant; the prepared FKM nano emulsion has uniform particle size distribution, no condensate in the preparation process, no adhesion to a kettle and short reaction time, and is beneficial to industrial production of high-elasticity fluororubber raw rubber.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a preparation method of high-elasticity fluororubber raw rubber.
Background
The fluororubber is widely applied to the fields of aerospace, automobiles, machinery, petrochemical industry and the like. For example as dynamic and static sealing materials for hydraulic and lubricating systems of aircraft; the sealing material is used as a sealing material for oil fields, and is used for cable oil pipelines and drilling equipment for the oil fields; the high-strength.
The applicant's prior application CN201410587149.4 discloses a preparation method of a heat-stable fluororubber raw rubber, which comprises the steps of putting 100 parts by weight of water, 0.02-0.2 part by weight of perfluorooctanoic acid, 0.1-0.2 part by weight of pH regulator, 0.06-0.2 part by weight of molecular weight regulator, 0.01-0.02 part by weight of initiator and 25-50 parts by weight of mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle, carrying out polymerization reaction at the reaction temperature of 20-80 ℃ and the reaction pressure of 0.5-0.8 MPa, recovering the mixed monomer after the reaction is finished, and carrying out freezing coagulation, washing, extrusion dehydration, vacuum drying and mastication molding on the obtained emulsion to obtain a heat-stable fluororubber product. The invention has the advantages of simple process and excellent high-temperature resistance and elasticity of the prepared product.
At present, many fluorine chemical manufacturers at home and abroad actively develop a substitute of PFOA (perfluorooctanoic acid), and carry out a great deal of work. For example: the zhonghao chen optical chemical research institute uses fluorine-containing olefin to prepare a surfactant containing an ether segment by oxidizing oxygen at low temperature in chinese patent document CN101648122A (application No. 200910092202.2); however, the surfactant obtained by this method contains a large amount of branched chains and is not well dispersed during the polymerization.
The Juhua corporation used a surfactant containing a fluoroether segment containing a chlorine atom in Chinese patent document CN102504063A (application No. 201110338501), but this surfactant had a high toxicity and could not completely satisfy the requirement of environmental friendliness.
The surfactants mentioned in U.S. Pat. Nos. 5789508, 4025709, 5688884, 5763552, etc., affect the product quality of the polymer during the polymerization reaction due to the molecular structure. In WO2005/042593 it is mentioned to use CF3(CF2)5COONH4 as a substitute for C8 for the dispersion process for the preparation of FKM.
The following technical problems exist: perfluorooctanoic acid (PFOA) is used as a CTFE, TFE and fluoroelastomer polymeric dispersant, and due to its persistence, bioaccumulation and toxicity, it is necessary to find alternative novel fluorosurfactants to reduce the amount of perfluorooctanoic acid (PFOA) used, which can have serious and irreversible effects on the environment and human health.
Disclosure of Invention
The invention discloses a preparation method of high-elasticity fluororubber raw rubber, and belongs to the technical field of chemical production. The novel fluorine-containing surfactant is adopted to partially replace perfluorooctanoic acid (PFOA), the stability of a dispersion system is good, and the dispersion system can be used as a polymerization dispersant.
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
1. a preparation method of high-elasticity fluororubber raw rubber is characterized by comprising the following steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 50-70% of the volume of the reaction kettle, adding 0.001-0.5 part of perfluorooctanoic acid, 0.015-0.5 part of auxiliary dispersing agent, 0.15-0.3 part of pH regulator, 0.05-0.3 part of molecular weight regulator and 0.01-0.1 part of initiator into 100 parts of water according to parts by weight, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 20-80 ℃;
(d) adding a vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer into a reaction kettle until the pressure of the reaction kettle is 0.5-0.8 MPa, and then adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the amount of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer reaches 25-50 parts by weight of the components and 100 parts of water, ending the reaction, recovering the mixed monomer, and performing freeze coagulation, washing, extrusion dehydration, vacuum drying and plastication molding on the obtained emulsion to obtain the high-elasticity fluororubber raw rubber product.
And further: according to the parts by weight: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 50-70 parts of vinylidene fluoride, 15-30 parts of perfluoropropylene and 15-40 parts of tetrafluoroethylene.
Furthermore, the addition amount of the perfluoro caprylic acid is 0.005-0.09 part,
furthermore, the addition amount of the auxiliary dispersant is 0.015 to 0.11 part,
and further: the initiator is one or a mixture of two of sodium sulfite, sodium phosphate and ammonium persulfate.
Further: the molecular weight regulator is one of trifluoromethanol, ethanol and diethyl malonate.
Further: the pH regulator is one of dipotassium hydrogen phosphate, sodium carbonate, sodium bicarbonate and sodium borate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 15-25 parts of polythiol, 0.01-0.33 part of borate, 100-120 parts of trifluoromethanol and 3-6 parts of sodium trifluoromethoxide into a reaction kettle by mass, introducing nitrogen, keeping the temperature at 50-57 ℃ for 0.5-2 h under the condition of stirring, adding 10-20 parts of perfluorosulfonyl vinyl ether, keeping the temperature at 50-57 ℃, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
And further: the amount of the perfluoropolyether surfactant in the step (b) is 0.02-0.1 part by mass; 3-8 parts of pH regulator aqueous solution, wherein the concentration of the pH regulator is 10-25%; in the step (d), the using amount of the initiator aqueous solution is 2 to 6 parts, the concentration of the initiator is 8 to 12 percent, and the molecular weight regulator is 0.001 to 0.01 part.
The reaction mechanism is as follows:
perfluorosulfonyl vinyl ether, ethylene glycol di (3-mercaptopropionate) and 1-vinyl-3-butyl imidazole tetrafluoroborate are subjected to Michael addition reaction to obtain the novel dispersing agent.
The technical effects are as follows:
the novel fluorine-containing surfactant is adopted to partially replace perfluorooctanoic acid, so that the dispersion system has good stability and can be used as a polymerization dispersant; the prepared low molecular weight FKM nano emulsion has the advantages of uniform particle size distribution, no condensate in the preparation process, no adhesion to a kettle, short reaction time and greatly improved tensile strength, and is favorable for industrial production of high-elasticity fluororubber raw rubber.
Drawings
FIG. 1 is a Fourier infrared spectrum of a sample of the fluororubber prepared in example 3.
Detailed Description
1. Mooney viscosity measurement
The test process is that the cavity of the mould is heated to constant temperature of (100 +/-1) DEG C, then the sample is put into the cavity of the mould and preheated for a certain time, the viscometer starts to work, when the rotor rotates, the scale value of the instrument is observed, and the displayed value is the Mooney viscosity value of the rubber, which is called Mooney viscosity for short.
2. Measurement of mechanical Properties
The tensile strength and elongation at break of the molded specimens were measured according to the method described in ASTM D638 using an universal tensile machine (ETM503A, Shenzhen Wan Messaging device Co., Ltd.). The experimental environment temperature is 23 +/-2 ℃, the stretching speed is 50mm/min +/-5 mm/min, and the clamp spacing is 24 mm.
3. Determination of decomposition temperature
A sample of PFA resin of about 10mg was taken, and heated from 50 ℃ to 600 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere using a thermogravimetric analyzer (TGA550, TA), and a thermogravimetric loss curve was recorded, and the temperature at which weight loss was 1% (wt) was taken as the decomposition temperature.
The invention is further illustrated by the following specific examples:
example 1
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 50 percent of the volume of the reaction kettle, adding 0.005kg of perfluorooctanoic acid, 0.015kg of auxiliary dispersing agent, 0.15kg of pH regulator, 0.05kg of molecular weight regulator and 0.01kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 60 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.5MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 25, ending the reaction, recovering the mixed monomer, and performing freeze coagulation, washing, extrusion dehydration, vacuum drying and plastication molding on the obtained emulsion to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 50kg of vinylidene fluoride, 15kg of perfluoropropene and 15kg of tetrafluoroethylene.
Further: the initiator is sodium sulfite.
Further: the molecular weight regulator is trifluoromethanol.
And further: the pH regulator is dipotassium hydrogen phosphate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 15kg of polythiol, 0.01kg of borate, 100kg of trifluoromethanol and 3kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 50 ℃ under the stirring condition, preserving the temperature for 0.5h, adding 10kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 50 ℃, preserving the temperature for 5h, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid additive is 1-vinyl-3-butylimidazole tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.02 kg; 3kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 25%; in the step (d), the using amount of the initiator aqueous solution is 2kg, the concentration of the initiator is 12 percent, and the molecular weight regulator is 0.001 kg.
Example 2
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 55 percent of the volume of the reaction kettle, adding 0.01kg of perfluorooctanoic acid, 0.04kg of auxiliary dispersing agent, 0.2kg of pH regulator, 0.1kg of molecular weight regulator and 0.02kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 60 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.6MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 30 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
And further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 55kg of vinylidene fluoride, 20kg of perfluoropropene and 20kg of tetrafluoroethylene.
Further: the initiator is sodium phosphate.
Further: the molecular weight regulator is ethanol.
Further: the pH regulator is sodium carbonate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 17kg of polythiol, 0.12kg of borate, 100kg of trifluoromethanol and 4kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 52 ℃ under the stirring condition, preserving the temperature for 1.0h, adding 12kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 52 ℃, preserving the temperature for 6h, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.1 kg; 3kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 20%; in the step (d), the using amount of the initiator aqueous solution is 3kg, the concentration of the initiator is 11 percent, and the molecular weight regulator is 0.003 kg.
Example 3
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 60 percent of the volume of the reaction kettle, adding 0.03kg of perfluorooctanoic acid, 0.06kg of auxiliary dispersing agent, 0.25kg of pH regulator, 0.2kg of molecular weight regulator and 0.04kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 60 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.7MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 35 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 60kg of vinylidene fluoride, 25kg of perfluoropropylene and 30kg of tetrafluoroethylene.
Further: the initiator is ammonium persulfate.
Further: the molecular weight regulator is diethyl malonate.
Further: the pH regulator is sodium bicarbonate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 20kg of polythiol, 0.18kg of borate, 110kg of trifluoromethanol and 4kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 55 ℃ under the stirring condition, preserving heat for 1.5 hours, adding 16kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 55 ℃, preserving heat for 6 hours, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.4 kg; 4kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 18%; in the step (d), the using amount of the initiator aqueous solution is 4kg, the initiator concentration is 10 percent, and the molecular weight regulator is 0.006 kg.
Example 4
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 65 percent of the volume of the reaction kettle, adding 0.05kg of perfluorooctanoic acid, 0.08kg of auxiliary dispersing agent, 0.25kg of pH regulator, 0.25kg of molecular weight regulator and 0.08kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 70 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.7MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 45 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 65kg of vinylidene fluoride, 25kg of perfluoropropylene and 30kg of tetrafluoroethylene.
Further: the initiator is a mixture of sodium sulfite and sodium phosphate in equal proportion.
Further: the molecular weight regulator is diethyl malonate.
Further: the pH regulator is sodium borate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 23kg of polythiol, 0.28kg of borate, 120kg of trifluoromethanol and 5kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 57 ℃ under the stirring condition, preserving the temperature for 2 hours, adding 18kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 57 ℃, preserving the temperature for 8 hours, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
And further: the borate in the preparation method of the dispersion aid additive is 1-vinyl-3-butylimidazole tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.8 kg; 6kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 16%; in the step (d), the using amount of the initiator aqueous solution is 5kg, the concentration of the initiator is 9 percent, and the molecular weight regulator is 0.008 kg.
Example 5
(a) Adding water into a reaction kettle, wherein the adding amount of the water is 70% of the volume of the reaction kettle, adding 0.09kg of perfluorooctanoic acid, 0.11kg of auxiliary dispersing agent, 0.3kg of pH regulator, 0.3kg of molecular weight regulator and 0.1kg of initiator into every 100kg of water according to parts by weight, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 80 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.8MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 50 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 70kg of vinylidene fluoride, 30kg of perfluoropropylene and 40kg of tetrafluoroethylene.
Further: the initiator is a mixture of sodium sulfite and ammonium persulfate in equal proportion.
Further: the molecular weight regulator is ethanol.
Further: the pH regulator is sodium borate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 25kg of polythiol, 0.33kg of borate, 120kg of trifluoromethanol and 6kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 57 ℃ under the stirring condition, preserving the temperature for 2 hours, adding 20kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 57 ℃, preserving the temperature for 8 hours, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.1 kg; 8kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 10%; in the step (d), the using amount of the initiator aqueous solution is 6kg, the concentration of the initiator is 8 percent, and the molecular weight regulator is 0.01 kg.
Comparative example 1
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 50 percent of the volume of the reaction kettle, adding 0.005kg of perfluorooctanoic acid, 0.015kg of auxiliary dispersing agent, 0.15kg of pH regulator, 0.05kg of molecular weight regulator and 0.01kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 20 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.5MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 25 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 50kg of vinylidene fluoride, 15kg of perfluoropropylene and 15kg of tetrafluoroethylene.
And further: the initiator is sodium sulfite.
Further: the molecular weight regulator is trifluoromethanol.
Further: the pH regulator is dipotassium hydrogen phosphate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 15kg of polythiol, 100kg of trifluorocarbinol and 3kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 50 ℃ under the stirring condition, keeping the temperature for 0.5h, adding 10kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 50 ℃, keeping the temperature for 5h, and distilling to remove the trifluorocarbinol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.02 kg; 3kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 25%; in the step (d), the using amount of the initiator aqueous solution is 2kg, the concentration of the initiator is 12 percent, and the molecular weight regulator is 0.001 kg.
Comparative example 2
A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps:
(a) adding water into a reaction kettle, wherein the adding amount of the water is 60 percent of the volume of the reaction kettle, adding 0.05kg of perfluorooctanoic acid, 0.06kg of auxiliary dispersing agent, 0.25kg of pH regulator, 0.25kg of molecular weight regulator and 0.05kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 60 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.6MPa, and then adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 35 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
Further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 60kg of vinylidene fluoride, 20kg of perfluoropropylene and 30kg of tetrafluoroethylene.
Further: the initiator is sodium phosphate.
And further: the molecular weight regulator is ethanol.
Further: the pH regulator is sodium bicarbonate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 20kg of polythiol, 0.22kg of borate and 110kg of trifluoromethanol into a reaction kettle, introducing nitrogen, controlling the temperature to be 55 ℃ under the stirring condition, keeping the temperature for 1.0h, adding 15kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 55 ℃, keeping the temperature for 6h, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
And further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
And further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.02 kg; 3kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 25%; in the step (d), the using amount of the initiator aqueous solution is 2kg, the concentration of the initiator is 12 percent, and the molecular weight regulator is 0.001 kg.
Comparative example 3
(a) Adding water into a reaction kettle, wherein the adding amount of the water is 70 percent of the volume of the reaction kettle, adding 0.09kg of perfluorooctanoic acid, 0.11kg of auxiliary dispersing agent, 0.3kg of molecular weight regulator and 0.1kg of initiator into every 100kg of water, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 80 ℃;
(d) adding a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene into a reaction kettle until the pressure of the reaction kettle is 0.8MPa, and adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the ratio of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer to 100kg of water reaches 50 by mass, the reaction is ended, the mixed monomer is recovered, and the obtained emulsion is subjected to freezing coagulation, washing, extrusion dehydration, vacuum drying and plastication molding to obtain the high-elasticity fluororubber raw rubber product.
And further: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 70kg of vinylidene fluoride, 30kg of perfluoropropylene and 40kg of tetrafluoroethylene.
And further: the initiator is ammonium persulfate.
Further: the molecular weight regulator is diethyl malonate.
Further: the pH regulator is sodium borate.
Further: the preparation method of the dispersion aid comprises the following steps:
adding 25kg of polythiol, 0.33kg of borate, 120kg of trifluoromethanol and 6kg of sodium trifluoromethoxide into a reaction kettle, introducing nitrogen, controlling the temperature to be 57 ℃ under the stirring condition, preserving heat for 2 hours, adding 20kg of perfluorosulfonyl vinyl ether, controlling the temperature to be 57 ℃, preserving heat for 8 hours, and distilling to remove the trifluoromethanol after the reaction is finished to obtain the fluoroether surfactant.
Further: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate) (CAS No. 22504-50-3).
Further: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate (CAS number: 1033461-44-7).
Further: the dosage of the perfluoropolyether surfactant in the step (b) is 0.02 kg; 3kg of pH regulator aqueous solution, wherein the concentration of the pH regulator is 25%; in the step (d), the using amount of the initiator aqueous solution is 2kg, the concentration of the initiator is 12 percent, and the molecular weight regulator is 0.001 kg.
The results of the performance tests of all the above examples and comparative examples are shown in the following table:
the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained desirable results. As can be seen from the table, the preparation method of the high-elasticity crude fluororubber adopted in the preferred embodiments 1-5 of the application can partially replace perfluorooctanoic acid with a novel fluorosurfactant; the prepared low molecular weight FKM nano emulsion has the advantages of uniform particle size distribution, no condensation product in the preparation process, no sticking to a kettle, short reaction time and contribution to industrial production of high-elasticity fluororubber raw rubber.
Claims (10)
1. A preparation method of high-elasticity fluororubber raw rubber comprises the following operation steps: (a) adding water into a reaction kettle, wherein the adding amount of the water is 50-70% of the volume of the reaction kettle, adding 0.001-0.5 part of perfluorooctanoic acid, 0.015-0.5 part of auxiliary dispersing agent, 0.15-0.3 part of pH regulator, 0.05-0.3 part of molecular weight regulator and 0.01-0.1 part of initiator into 100 parts of water according to parts by weight, and uniformly stirring for later use;
(b) adding a perfluoropolyether surfactant and a pH regulator aqueous solution into a reaction kettle according to the determined weight components;
(c) deoxidizing the reaction kettle, and then heating to 20-80 ℃;
(d) adding a vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer into a reaction kettle until the pressure of the reaction kettle is 0.5-0.8 MPa, and then adding an initiator aqueous solution and a molecular weight regulator according to determined weight components to start a polymerization reaction;
(e) in the polymerization reaction process, a mixed monomer of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene is additionally added to maintain the constant pressure of the reaction kettle;
(f) and when the amount of the added vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer reaches 25-50 parts by weight of the components and 100 parts of water, ending the reaction, recovering the mixed monomer, and performing freeze coagulation, washing, extrusion dehydration, vacuum drying and plastication molding on the obtained emulsion to obtain the high-elasticity fluororubber raw rubber product.
2. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: according to the parts by weight: the vinylidene fluoride, tetrafluoroethylene and perfluoropropylene mixed monomer comprises the following components: 50-70 parts of vinylidene fluoride, 15-30 parts of perfluoropropylene and 15-40 parts of tetrafluoroethylene.
3. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the initiator is one or a mixture of two of sodium sulfite, sodium phosphate and ammonium persulfate.
4. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the addition amount of the perfluoro caprylic acid is 0.005-0.09 part.
5. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the addition amount of the auxiliary dispersing agent is 0.015-0.11 part.
6. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the molecular weight regulator is one of trifluoromethanol, ethanol and diethyl malonate.
7. The method for preparing high-elasticity fluororubber according to claim 1, characterized in that: the pH regulator is one of dipotassium hydrogen phosphate, sodium carbonate, sodium bicarbonate and sodium borate.
8. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the preparation method of the dispersion aid comprises the following steps:
adding 15-25 parts of polythiol, 0.01-0.33 part of borate, 100-120 parts of trifluoromethanol and 3-6 parts of sodium trifluoromethoxide into a reaction kettle by mass, introducing nitrogen, then, controlling the temperature to be 50-57 ℃ under the stirring condition, preserving the heat for 0.5-2 h, then, adding 10-20 parts of perfluorosulfonyl vinyl ether, controlling the temperature to be 50-57 ℃, preserving the heat for 5-8 h, and removing the trifluoromethanol by distillation after the reaction is finished to obtain the fluoroether surfactant.
9. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the polythiol in the preparation method of the dispersion aid is ethylene glycol di (3-mercaptopropionate).
10. The method for preparing high-elasticity crude fluororubber according to claim 1, wherein the method comprises the following steps: the borate in the preparation method of the dispersion aid is 1-vinyl-3-butylimidazolium tetrafluoroborate.
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| US20140357821A1 (en) * | 2011-12-29 | 2014-12-04 | Shaochun Zhao | Low-temperature-resistant fluorine-containing elastomer and preparation method therefor |
| CN104497189A (en) * | 2014-10-28 | 2015-04-08 | 浙江巨圣氟化学有限公司 | Preparation method of thermally-stable raw fluorubber |
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| CN103709306A (en) * | 2013-12-30 | 2014-04-09 | 江苏梅兰化工有限公司 | Nano emulsion of peroxide vulcanized fluororubber and polymerization method thereof |
| CN104497189A (en) * | 2014-10-28 | 2015-04-08 | 浙江巨圣氟化学有限公司 | Preparation method of thermally-stable raw fluorubber |
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