CN110818825A - Peroxide-curable fluorine-containing elastomer and preparation method thereof - Google Patents

Peroxide-curable fluorine-containing elastomer and preparation method thereof Download PDF

Info

Publication number
CN110818825A
CN110818825A CN201810892524.4A CN201810892524A CN110818825A CN 110818825 A CN110818825 A CN 110818825A CN 201810892524 A CN201810892524 A CN 201810892524A CN 110818825 A CN110818825 A CN 110818825A
Authority
CN
China
Prior art keywords
vinyl ether
vinylidene fluoride
reactor
hexafluoropropylene
comonomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810892524.4A
Other languages
Chinese (zh)
Inventor
曾波
汪仲权
王先荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Original Assignee
Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd filed Critical Zhonghao Chenguang Research Institute of Chemical Industry Co Ltd
Priority to CN201810892524.4A priority Critical patent/CN110818825A/en
Publication of CN110818825A publication Critical patent/CN110818825A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
    • 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
    • C08F214/184—Monomers containing fluorine with fluorinated vinyl ethers
    • 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
    • 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1408—Monomers containing halogen
    • 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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether

Abstract

The present invention relates to a peroxide curable fluoroelastomer and a process for preparing the same. The preparation method comprises the following steps: adding water into the reactor, and evacuating to make the oxygen content not greater than 30 ppm; heating to 60-100 ℃ until the temperature of the reaction environment reaches; adding a comonomer into a reactor until the pressure in the reactor reaches 1-5 Mpa, and then respectively adding an emulsifier, a free radical initiator and a chain transfer agent to initiate polymerization; continuously adding a comonomer in the reaction process, maintaining the pressure in the reactor at 1-5 Mpa until the target input amount is reached, and stopping the reaction to obtain an elastomer emulsion; coagulating, washing and drying the elastomer emulsion to obtain the fluorine-containing elastomer capable of being vulcanized by peroxide; the obtained fluororubber has excellent fluidity and can be processed by adopting extrusion and injection molding processes. The vulcanized product has the properties of high strength, low permanent compression set, excellent hot air aging resistance and the like.

Description

Peroxide-curable fluorine-containing elastomer and preparation method thereof
Technical Field
The invention relates to the technical field of fluorine chemical industry, in particular to a fluorine-containing elastomer capable of being vulcanized by peroxide and a preparation method thereof.
Background
Fluoroelastomers are widely used for sealing materials, containers and hoses because of their excellent heat resistance, oil resistance and chemical resistance. Common peroxide curable fluoroelastomers include two major classes, vinylidene fluoride-based copolymerized elastomers and tetrafluoroethylene-based copolymerized monomers. Such as vinylidene fluoride (VDF), perfluoropropylene (HFP), Tetrafluoroethylene (TFE), and bromine-containing olefin copolymer elastomers.
To achieve the physical properties necessary for a wide range of needs, the resulting fluoroelastomers must be crosslinked for use. The curing system is a mixture of an organic peroxide and a multifunctional unsaturated coagent. And the crosslinking site is the "I" or "Br" atom of the "C-I" or "C-Br" bond on the fluoroelastomer.
According to the patent and literature reports at home and abroad, the vulcanization point monomer of the fluororubber mainly used for peroxide vulcanization is mainly bromine-containing olefin, iodine-containing olefin, non-conjugated diene, cyano-containing olefin and the like, and bromine and iodine atoms, double bonds of 'C ═ C', or-CN are introduced to the molecular chain of the fluoroelastomer in the polymerization process to play a role of a crosslinking point in the peroxide vulcanization process.
Disclosure of Invention
The invention aims to provide a fluorine-containing elastomer capable of being vulcanized by peroxide and a preparation method thereof. The preparation method adopts vinylidene fluoride (VDF), Tetrafluoroethylene (TFE), perfluoropropylene (HFP), perfluoroalkyl vinyl ether (PAVE) and perfluoroalkoxy alkyl vinyl ether (MVE) as main comonomers, adopts iodo perfluoroolefin as a vulcanization point monomer, and adopts iodo alkane as a chain transfer agent. Under certain temperature and pressure conditions, obtaining fluororubber emulsion through emulsion polymerization, and obtaining the fluorine-containing elastomer vulcanized by a peroxide vulcanization system after the emulsion is coagulated, washed and dried.
The method specifically comprises the following steps:
1) adding water into the reactor, and evacuating the reactor to make the oxygen content not greater than 30 ppm; heating to 60-100 ℃ until the temperature of the reaction environment reaches;
2) adding a comonomer except for a vulcanization point monomer into a reactor to enable the pressure of the comonomer to reach 1-5 Mpa, and then respectively adding the vulcanization point monomer, an emulsifier, a free radical initiator and a chain transfer agent to initiate polymerization;
3) continuously adding a comonomer except a vulcanization point monomer in the reaction process, maintaining the pressure in a reactor at 1-5 Mpa until the target adding amount is reached, and stopping the reaction to obtain an elastomer emulsion;
4) and coagulating, washing and drying the elastomer emulsion to obtain the fluorine-containing elastomer capable of being vulcanized by peroxide.
Wherein the comonomer consists of vinylidene fluoride, one or more selected from hexafluoropropylene, tetrafluoroethylene, perfluoroalkyl vinyl ether and perfluoroalkoxy vinyl ether, and a vulcanization point monomer;
the copolymerization unit is specifically as follows:
(A) a first comonomer vinylidene fluoride (VDF);
(B) at least one second fluoromonomer other than vinylidene fluoride, such as Hexafluoropropylene (HFP), Tetrafluoroethylene (TFE), perfluoroalkyl vinyl ether (PAVE), perfluoroalkoxy vinyl ether (MVE), and the like;
(C) the cure site monomer is iodo perfluoroolefin (CSM).
The invention adopts iodo perfluoroolefin as a vulcanization point monomer and an iodine-containing chain transfer agent RfIX(Rf1-6 perfluoroalkyl groups, and X is 1-3) to introduce an 'I' vulcanization point into the middle and the end position of a molecular chain of the fluorine-containing elastomer, and the 'I' vulcanization point plays a role of a crosslinking point in the vulcanization process. Wherein, in the preparation process, the vulcanization point monomer is added all at once, which is different from the adding time and mode of other comonomers.
Preferably, the comonomer, except the vulcanization point monomer, specifically is: one of vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene, vinylidene fluoride/perfluoroalkyl vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkoxy vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether, vinylidene fluoride/perfluoroalkoxy vinyl ether, vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether, vinylidene fluoride/tetrafluoroethylene/perfluoroalkoxy vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether;
more preferably, the comonomer is vinylidene fluoride/hexafluoropropylene with a molar ratio of 50-90: 10-50 except for a vulcanization point monomer; further preferably vinylidene fluoride/hexafluoropropylene with the molar ratio of 60-80: 20-40;
or vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene in a molar ratio of 45-70: 18-34: 12-22;
or vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether with the molar ratio of 60-80: 10-30,
or vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether with the molar ratio of 80-50: 2-10: 10-48.
The invention further provides that in step 1), when water is added, the pH value can be adjusted according to the situation, and the pH buffering agent for adjusting the pH value can adopt a conventional reagent, preferably dipotassium hydrogen phosphate.
The invention further provides that the sulfuration point monomer is iodo perfluoroolefin;
preferably, the iodo perfluoroolefin is selected from one or more of iodo trifluoroethylene, perfluoro iodo ethyl vinyl ether, perfluoro iodo ethoxy propyl vinyl ether, perfluoro iodo methoxymethyl vinyl ether, and perfluoro iodo-3, 5-dioxahexyl vinyl ether;
more preferably, the mass of the cure site monomer is 0.1 to 4%, and still more preferably 0.4 to 3% of the mass of the comonomer.
The invention further provides that the chain transfer agent is iodoalkane;
preferably, the iodoalkane is selected from α, omega-diiodoalkane and α, omega-diiodoperfluoroalkane, such as one or more of diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodopentane, 1, 4-diiodoperfluoro, preferably 1, 4-diiodoperfluorobutane
More preferably, the mass of the chain transfer agent is 0.1 to 2% of the mass of the comonomer.
The invention further provides that the emulsifier is perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1;
preferably, the emulsifier accounts for 0.05-0.6% of the mass of the comonomer;
the free radical initiator is selected from one or more of ammonium persulfate and potassium persulfate.
Preferably, the free radical initiator accounts for 0.05-0.6% of the mass of the comonomer.
The invention further provides that a suitable polymerization pressure is preferred, wherein the polymerization pressure is too low to allow the reaction to proceed, and too high a polymerization pressure results in a product with a high molecular weight and a high Mooney viscosity. Preferably, the pressure is 1.6-2.8 MPa.
Preferably, the temperature is 70-90 ℃.
The invention further provides that the agglomeration, washing and drying are carried out in a conventional manner. Preferably, the coagulation is carried out by specifically using a potassium chloride aqueous solution; the drying is carried out for 10-18h in vacuum at the temperature of 70-90 ℃.
The invention provides a preferable scheme, and the preparation method comprises the following steps:
1) adding water into the reactor, evacuating the reactor to ensure that the oxygen content is not more than 30ppm, and heating to the reaction temperature of 60-100 ℃;
2) adding a comonomer except a vulcanization point monomer into a reactor, enabling the pressure in the reactor to reach 1-5 Mpa, and respectively adding a mixture of perfluoropolyether peroxide and sodium octyl sulfonate, perfluoroalkyl iodide vinyl ether, an ammonium persulfate aqueous solution and 1, 4-diiodoperfluorobutane in a mass ratio of 1:1 to initiate polymerization;
the comonomers except the vulcanization point monomer are specifically as follows: vinylidene fluoride/hexafluoropropylene with a molar ratio of 50-90: 10-50; or vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene in a molar ratio of 45-70: 18-34: 12-22; or vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether with the molar ratio of 60-80: 10-30; or vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether with the molar ratio of 80-50: 2-10: 10-48;
3) continuously adding a comonomer except a vulcanization point monomer in the reaction process, maintaining the pressure in a reactor at 1-5 Mpa until the target adding amount is reached, and stopping the reaction to obtain an elastomer emulsion;
4) and coagulating, washing and drying the elastomer emulsion to obtain the fluorine-containing elastomer capable of being vulcanized by peroxide.
The fluororubber prepared by the preparation method has excellent fluidity and can be processed by adopting extrusion and injection molding processes. The vulcanized product has the properties of high strength, low permanent compression set, excellent hot air aging resistance and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF/HFP (60/40 mol ratio) is added into a reaction kettle by a compressor, the pressure is increased to 1.5MPa at 80 ℃, 40g of iodotrifluoroethylene is added, 20g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 25g of chain transfer agent ICF is added when the pressure of the reaction kettle is reduced to 1.4MPa2CF2While adding a monomer mixture of VDF/HFP 60/40 (molar ratio), the pressure in the reactor was kept at 1.5 MPa.
3) The reaction was continued and stopped when the VDF/HFP charge reached 1.5 kg. .
4) Coagulating with potassium chloride water solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 2
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) charging mixed monomer of VDF/HFP 80/20 (molar ratio) into a reaction kettle by a compressor, increasing the pressure to 1.5MPa at 80 ℃, adding 40g of perfluoro iodo ethyl vinyl ether, pressing 20g of 15% (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization, and adding 20g of chain transfer agent ICF when the pressure of the reaction kettle is reduced to 1.4MPa2CF2While adding a monomer mixture of VDF/HFP 80/20 (molar ratio), the pressure in the reactor was kept at 1.5 MPa.
3) The reaction was continued and stopped when the VDF/HFP charge reached 1.5 kg. .
4) Coagulating with potassium chloride water solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 3
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF/HFP/TFE 65/20/15 (molar ratio) was charged into a reactor by a compressor, the pressure was increased to 1.8MPa at 80 ℃, and 30g of perfluoroiodoethoxypropyl ethylene was addedAdding alkyl ether, then pressing 10g of 15% (wt) ammonium persulfate aqueous solution into the reactor by a metering pump to initiate polymerization reaction, and adding 24g of chain transfer agent ICF when the pressure of the reactor is reduced to 1.7MPa2CF2CF2CF2I, simultaneously adding mixed monomers of VDF/HFP/TFE (molar ratio) 65/20/15, and keeping the pressure in the reaction kettle at 1.8 Mpa;
3) the reaction is continuously carried out, and the reaction is stopped when the feeding amount of VDF/HFP/TFE reaches 1.5 kg;
4) coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 4
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF/HFP/PMVE 70/20/10 (molar ratio) is added into a reaction kettle by a compressor, the pressure is increased to 2.8MPa at 80 ℃, 40g of perfluoro iodoethoxypropyl vinyl ether is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, and 24g of chain transfer agent ICF is added when the pressure of the reaction kettle is reduced to 2.7MPa2CF2CF2CF2I, and meanwhile, mixed monomers of VDF/HFP/PMVE 70/20/10 (molar ratio) are added, and the pressure in the reaction kettle is kept at 2.8 MPa.
3) The reaction is continuously carried out, and the reaction is stopped when the feeding amount of VDF/HFP/PMVE reaches 1.5 kg;
4) coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 5
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF/HFP/PMVE 80/10/10 (molar ratio) was charged into a reactor by a compressor, the pressure was increased to 2.8MPa at 80 ℃, 40g of perfluoroiodo-3, 5-dioxahexyl vinyl ether was added, 10g of a 15% (wt) aqueous ammonium persulfate solution was then introduced by a metering pump to initiate polymerization, and 25g of a chain transfer agent ICF was added when the pressure in the reactor was decreased to 2.7MPa2CF2CF2CF2I, and meanwhile, mixed monomers of VDF/HFP/PMVE 80/10/10 (molar ratio) are added, and the pressure in the reaction kettle is kept at 2.8 MPa.
3) The reaction was continued and stopped when the VDF/HFP/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 6
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 9g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, TFE and PMVE 80:2:18 (molar ratio) was charged into a reactor by a compressor, the pressure was raised to 1.0MPa at 90 ℃, 45g of perfluoroiodo-3, 5-dioxahexyl vinyl ether was added, 10g of a 15 wt% aqueous ammonium persulfate solution was then introduced by a metering pump to initiate polymerization, and when the pressure in the reactor was lowered to 0.9MPa, 30g of a chain transfer agent ICF was added2CF2CF2CF2I, and simultaneously adding mixed monomers of VDF, TFE and PMVE (molar ratio) of 80:2:18, and keeping the pressure in the reaction kettle at 1.0 MPa.
3) The reaction was continued and stopped when the VDF/TFE/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 7
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 9g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF: HFP: TFE 70:18:12 (molar ratio) was charged into a reactor by a compressor, the pressure was raised to 2.3MPa at 90 ℃, 45g of perfluoroiodo-3, 5-dioxahexyl vinyl ether was added, 10g of a 15 wt% aqueous ammonium persulfate solution was then introduced by a metering pump to initiate polymerization, and when the pressure in the reactor was lowered to 2.2MPa, 30g of a chain transfer agent ICF was added2CF2CF2CF2And I, simultaneously adding mixed monomers of VDF, HFP, TFE 70:18:12 (molar ratio), and keeping the pressure in the reaction kettle at 2.3 MPa.
3) The reaction was continued and stopped when the VDF/HFP/TFE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 8
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 1.5g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) the reaction kettle is charged with VDF TFE PMVE 60:10:30 (molar ratio) by a compressorMixing monomers, increasing the pressure to 2.5MPa at 80 ℃, adding 15g of trifluoroiodoethylene, then pressing 10g of 15 percent (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization reaction, and adding 20g of chain transfer agent ICF when the pressure of a reaction kettle is reduced to 2.4MPa2CF2I, and simultaneously adding mixed monomers of VDF, TFE and PMVE in a molar ratio of 60:10:30, and keeping the pressure in the reaction kettle at 2.5 MPa.
3) The reaction was continued and stopped when the VDF/TFE/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 9
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 2g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, HFP and TFE 45:33:22 (molar ratio) is fed into a reaction kettle by a compressor, the pressure is increased to 2.8MPa at 60 ℃, 6g of trifluoroiodoethylene is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 10g of chain transfer agent 1, 4-diiodobutane is added when the pressure of the reaction kettle is reduced to 2.7MPa, and the mixed monomer of VDF, HFP and TFE 45:33:22 (molar ratio) is supplemented, so that the pressure in the reaction kettle is kept to be 2.8 MPa.
3) The reaction was continued and stopped when the VDF/HFP/TFE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 10
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 6g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, TFE and PMVE in a molar ratio of 50:2:48 is fed into a reaction kettle by a compressor, the pressure is increased to 3.0MPa at 60 ℃, 45g of perfluoro iodoethoxyvinyl ether is added, 10g of a 15 wt% ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, when the pressure of the reaction kettle is reduced to 2.9MPa, 10g of chain transfer agent diiodomethane is added, and mixed monomer of VDF, TFE and PMVE in a molar ratio of 50:2:48 is supplemented, and the pressure in the reaction kettle is kept to be 3.0 MPa.
3) The reaction was continued and stopped when the VDF/TFE/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 11
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 6g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer with VDF and HFP being 90:10 (molar ratio) is added into a reaction kettle by a compressor, the pressure is increased to 3.5MPa at 60 ℃, 40g of perfluoro iodo ethoxy vinyl ether is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 5g of chain transfer agent diiodomethane is added when the pressure of the reaction kettle is reduced to 3.4MPa, and simultaneously the mixed monomer with VDF and HFP being 90:10 (molar ratio) is supplemented, so that the pressure in the reaction kettle is kept to be 3.5 MPa.
3) The reaction was continued and stopped when the VDF/HFP charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 12
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 7g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer with VDF and HFP being 70:30 (molar ratio) is added into a reaction kettle by a compressor, the pressure is increased to 2.5MPa at 80 ℃, 20g of perfluoro iodo ethoxy vinyl ether is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, when the pressure of the reaction kettle is reduced to 2.4MPa, 3g of chain transfer agent diiodomethane is added, and simultaneously the mixed monomer with VDF and HFP being 70:30 (molar ratio) is supplemented, so that the pressure in the reaction kettle is kept to be 2.5 MPa.
3) The reaction was continued and stopped when the VDF/HFP charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 13
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 7g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, HFP and TFE 60:20:20 (molar ratio) was fed into a reactor by a compressor, the pressure was increased to 1.5MPa at 90 ℃, 1.5g of trifluoroiodoethylene was fed, 10g of a 15 wt% aqueous ammonium persulfate solution was introduced into the reactor by a metering pump to initiate polymerization, and when the pressure in the reactor was decreased to 1.4MPa, 2g of diiodomethane as a chain transfer agent was fed and the mixed monomer of VDF, HFP and TFE 60:20:20 (molar ratio) was further fed, thereby maintaining the pressure in the reactor at 1.5 MPa.
3) The reaction was continued and stopped when the VDF/HFP/TFE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 14
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 8g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, HFP and TFE in a molar ratio of 50:30:20 is fed into a reaction kettle by a compressor, the pressure is increased to 2.0MPa at 85 ℃, 60g of perfluoro iodomethoxymethyl vinyl ether is added, 10g of a 15 wt% ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 2g of chain transfer agent diiodomethane is added when the pressure of the reaction kettle is reduced to 1.9MPa, and the mixed monomer of VDF, HFP and TFE in a molar ratio of 50:30:20 is supplemented to keep the pressure in the reaction kettle at 2.0 MPa.
3) The reaction was continued and stopped when the VDF/HFP/TFE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 15
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 9g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, HFP and TE in a molar ratio of 50:30:20 is added into a reaction kettle by a compressor, the pressure is increased to 5.0MPa at 60 ℃, 45g of perfluoro iodo ethoxy vinyl ether is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 1.5g of chain transfer agent diiodomethane is added when the pressure of the reaction kettle is reduced to 4.9MPa, and the mixed monomer of VDF, HFP and TE in a molar ratio of 50:30:20 is supplemented at the same time, so that the pressure in the reaction kettle is kept to be 5.0 MPa.
3) The reaction was continued, and when the amount of VDF/HFP/TE charged reached 1.5kg, the reaction was stopped.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 16
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 6g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) charging mixed monomer of VDF: HFP: PMVE 60:30:10 (molar ratio) into a reaction kettle by a compressor, raising the pressure to 2.8MPa at 60 ℃, adding 35g of perfluoro iodo ethoxy vinyl ether, then pressing 10g of 15% (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization, and adding 20g of chain transfer agent ICF when the pressure of the reaction kettle is reduced to 2.7MPa2CF2I, simultaneously adding mixed monomers of VDF, HFP and PMVE in a molar ratio of 60:30:10, and keeping the pressure in the reaction kettle at 2.8 MPa.
3) The reaction was continued and stopped when the VDF/HFP/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Example 17
This example provides a process for preparing a peroxide curable fluoroelastomer, comprising the steps of:
1) adding 3L of deionized water, 2g of dipotassium hydrogen phosphate and 6g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 5L stainless steel reaction kettle with a stirrer, and repeatedly pressurizing with nitrogen, evacuating and degassing to ensure that the oxygen content is not higher than 30 ppm;
2) a mixed monomer of VDF, HFP and PMVE in a molar ratio of 60:10:30 is added into a reaction kettle by a compressor, the pressure is increased to 2.8MPa at 70 ℃, 35g of perfluoro iodo ethoxy vinyl ether is added, 10g of 15 percent (wt) ammonium persulfate aqueous solution is pressed in by a metering pump to initiate polymerization, 20g of chain transfer agent ICF is added when the pressure of the reaction kettle is reduced to 2.7MPa2CF2I, simultaneously adding mixed monomers of VDF, HFP and PMVE in a molar ratio of 60:10:30, and keeping the pressure in the reaction kettle at 2.8 MPa.
3) The reaction was continued and stopped when the VDF/HFP/PMVE charge reached 1.5 kg.
4) Coagulating with magnesium chloride aqueous solution, washing, and drying in 80 deg.C vacuum oven for 14 hr to obtain 1.5kg elastomer product.
Test examples
The fluoroelastomer for peroxide vulcanization obtained in examples 1 to 17 was examined and the results are shown in the following table:
TABLE 1
Figure BDA0001757318030000151
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A process for the preparation of a peroxide curable fluoroelastomer, comprising the steps of:
1) adding water into the reactor, evacuating the reactor to ensure that the oxygen content is not more than 30ppm, and heating to the reaction temperature of 60-100 ℃;
2) adding a comonomer except a vulcanization point monomer into a reactor, enabling the pressure of the comonomer to reach 1-5 Mpa, and then respectively adding the vulcanization point monomer, an emulsifier, a free radical initiator and a chain transfer agent to initiate polymerization;
3) continuously adding a comonomer except a vulcanization point monomer in the reaction process, maintaining the pressure in a reactor at 1-5 Mpa until the target adding amount is reached, and stopping the reaction to obtain an elastomer emulsion;
4) coagulating, washing and drying the elastomer emulsion to obtain the fluorine-containing elastomer capable of being vulcanized by peroxide;
the comonomer consists of vinylidene fluoride, one or more of hexafluoropropylene, tetrafluoroethylene, perfluoroalkyl vinyl ether and perfluoroalkoxy vinyl ether, and a vulcanization point monomer.
2. The preparation method according to claim 1, wherein the comonomers, in addition to the cure site monomer, are specifically: one of vinylidene fluoride/hexafluoropropylene, vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene, vinylidene fluoride/perfluoroalkyl vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkoxy vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether, vinylidene fluoride/perfluoroalkoxy vinyl ether, vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether, vinylidene fluoride/tetrafluoroethylene/perfluoroalkoxy vinyl ether, vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether;
preferably, the comonomer is vinylidene fluoride/hexafluoropropylene with a molar ratio of 50-90: 10-50 except for a vulcanization point monomer;
or vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene in a molar ratio of 45-70: 18-34: 12-22;
or vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether with the molar ratio of 60-80: 10-30;
or vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether with the molar ratio of 80-50: 2-10: 10-48.
3. The production method according to claim 1 or 2, wherein the vulcanization site monomer is iodoperfluoroolefin;
preferably, the iodo perfluoroolefin is selected from one or more of iodo trifluoroethylene, perfluoro iodo ethyl vinyl ether, perfluoro iodo ethoxy vinyl ether, perfluoro iodo ethoxypropyl vinyl ether, perfluoro iodo methoxymethyl vinyl ether, and perfluoro iodo-3, 5-dioxahexyl vinyl ether.
4. The method according to claim 3, wherein the mass of the cure site monomer is 0.1 to 4%, preferably 0.4 to 3%, of the total mass of the comonomers.
5. The preparation method according to any one of claims 1 to 4, wherein the chain transfer agent is an alkyl iodide, wherein the alkyl iodide is one or more of α, omega-diiodoalkane, α, omega-diiodoperfluoroalkane;
preferably, the chain transfer agent is selected from one or more of diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodopentane and 1, 4-diiodoperfluoro;
more preferably, the mass of the chain transfer agent is 0.1% to 2% of the mass of the comonomer.
6. The preparation method according to any one of claims 1 to 5, wherein the emulsifier is perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1;
preferably, the emulsifier accounts for 0.05-0.6% of the mass of the comonomer.
7. The preparation method according to any one of claims 1 to 6, wherein the radical initiator is selected from one or more of ammonium persulfate and potassium persulfate;
preferably, the free radical initiator accounts for 0.05-0.6% of the mass of the comonomer.
8. The method of any one of claims 1 to 7, wherein the pressure is 1.6 to 2.8MPa and/or the temperature is 70 to 90 ℃.
9. The method according to any one of claims 1 to 8, comprising the steps of:
1) adding water into the reactor, evacuating the reactor to ensure that the oxygen content is not more than 30ppm, and heating to the reaction temperature of 60-100 ℃;
2) adding a comonomer except a vulcanization point monomer into a reactor, enabling the pressure in the reactor to reach 1-5 Mpa, and respectively adding a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1:1, perfluoroalkyl vinyl ether, an ammonium persulfate aqueous solution and 1, 4-diiodoperfluorobutane to initiate polymerization;
the comonomers except the vulcanization point monomer are specifically as follows: vinylidene fluoride/hexafluoropropylene with a molar ratio of 50-90: 10-50; or vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene in a molar ratio of 45-70: 18-34: 12-22; or vinylidene fluoride/hexafluoropropylene/perfluoroalkyl vinyl ether with a molar ratio of 60-80: 10-30, or vinylidene fluoride/tetrafluoroethylene/perfluoroalkyl vinyl ether with a molar ratio of 80-50: 2-10: 10-48;
3) continuously adding a comonomer except a vulcanization point monomer in the reaction process, maintaining the pressure in a reactor at 1-5 Mpa until the target adding amount is reached, and stopping the reaction to obtain an elastomer emulsion;
4) and coagulating, washing and drying the elastomer emulsion to obtain the fluorine-containing elastomer capable of being vulcanized by peroxide.
10. A peroxide-curable fluoroelastomer obtained by the production process according to any one of claims 1 to 9.
CN201810892524.4A 2018-08-07 2018-08-07 Peroxide-curable fluorine-containing elastomer and preparation method thereof Pending CN110818825A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810892524.4A CN110818825A (en) 2018-08-07 2018-08-07 Peroxide-curable fluorine-containing elastomer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810892524.4A CN110818825A (en) 2018-08-07 2018-08-07 Peroxide-curable fluorine-containing elastomer and preparation method thereof

Publications (1)

Publication Number Publication Date
CN110818825A true CN110818825A (en) 2020-02-21

Family

ID=69534050

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810892524.4A Pending CN110818825A (en) 2018-08-07 2018-08-07 Peroxide-curable fluorine-containing elastomer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110818825A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111333766A (en) * 2020-04-24 2020-06-26 四川道弘科技有限公司 Binary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN111363076A (en) * 2020-04-24 2020-07-03 四川道弘科技有限公司 Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN111875732A (en) * 2020-08-18 2020-11-03 山东非金属材料研究所 Low-temperature-resistant fluororubber and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037921A (en) * 1990-03-01 1991-08-06 E. I. Du Pont De Nemours And Company Base resistant fluoroelastomers with improved processibility and curability
CN103342772A (en) * 2013-07-12 2013-10-09 中昊晨光化工研究院有限公司 Preparation method of fluorinated elastomer capable of being vulcanized by using peroxide
CN104448095A (en) * 2014-12-15 2015-03-25 中昊晨光化工研究院有限公司 Preparation method of fluororubber capable of being vulcanized by peroxide
CN104558364A (en) * 2014-12-31 2015-04-29 山东华夏神舟新材料有限公司 Fluoroelastomer and preparation method thereof
CN107868163A (en) * 2016-09-27 2018-04-03 中昊晨光化工研究院有限公司 A kind of low temperature resistant perfluoroether elastomer and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037921A (en) * 1990-03-01 1991-08-06 E. I. Du Pont De Nemours And Company Base resistant fluoroelastomers with improved processibility and curability
CN103342772A (en) * 2013-07-12 2013-10-09 中昊晨光化工研究院有限公司 Preparation method of fluorinated elastomer capable of being vulcanized by using peroxide
CN104448095A (en) * 2014-12-15 2015-03-25 中昊晨光化工研究院有限公司 Preparation method of fluororubber capable of being vulcanized by peroxide
CN104558364A (en) * 2014-12-31 2015-04-29 山东华夏神舟新材料有限公司 Fluoroelastomer and preparation method thereof
CN107868163A (en) * 2016-09-27 2018-04-03 中昊晨光化工研究院有限公司 A kind of low temperature resistant perfluoroether elastomer and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111333766A (en) * 2020-04-24 2020-06-26 四川道弘科技有限公司 Binary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN111363076A (en) * 2020-04-24 2020-07-03 四川道弘科技有限公司 Ternary peroxide fluororubber and preparation method thereof, and intelligent wearing material and preparation method thereof
CN111875732A (en) * 2020-08-18 2020-11-03 山东非金属材料研究所 Low-temperature-resistant fluororubber and preparation method thereof

Similar Documents

Publication Publication Date Title
US7812086B2 (en) Fluorinated elastomer latex, its production method, fluorinated elastomer and fluororubber molded product
JP5265688B2 (en) Process for producing clean fluoropolymers
WO2015003451A1 (en) Method of preparing fluoroelastomer capable of being vulcanized by using peroxide
CN110903428B (en) Low-temperature-resistant fluoroether rubber and preparation method and application thereof
CN104448095B (en) A kind of preparation method of the fluorubber of peroxide curable
JPS6212734A (en) Novel fluorovinyl ether and copolymer containing same
CN110818825A (en) Peroxide-curable fluorine-containing elastomer and preparation method thereof
WO2013097477A1 (en) Low-temperature-resistant fluorine-containing elastomer and preparation method therefor
EP2315787A2 (en) Azide-containing fluoropolymers and their preparation
CN110713564A (en) Wide-temperature-range perfluoroether rubber and synthesis method thereof
CN104558364B (en) Fluoroelastomer and preparation method thereof
CN110684141A (en) Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content
CN114106495A (en) Modified perfluoroether fluororubber and preparation method and application thereof
JPH1067821A (en) Fluororubber, its manufacture and use, and manufacture of molding and/or coating of fluororubber
JPH0660120B2 (en) New fluorovinyl ether
CN103739767B (en) A kind of preparation method of fluoroelastomer
CN114230737B (en) Perfluoro ether fluororubber and preparation method and application thereof
CN116162199A (en) Fluororubber raw rubber and preparation method thereof
CN110760026B (en) Synthesis method of tetrafluoroethylene-propylene rubber and tetrafluoroethylene-propylene rubber thereof
CN114106496B (en) Rubber material and preparation method and application thereof
CN116143967A (en) Fluoroelastomer for lithium battery sealing and preparation method thereof
CN116063640A (en) High Wen Quanfu-resistant ether fluororubber and preparation method thereof
CN111072839A (en) Large-crosslinking-density rapidly-vulcanized fluorine-containing elastomer and preparation method thereof
CN113861328A (en) Peroxide vulcanized fluororubber with low compression deformation and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200221

RJ01 Rejection of invention patent application after publication