CN110903428A - Low-temperature-resistant fluoroether rubber and preparation method and application thereof - Google Patents
Low-temperature-resistant fluoroether rubber and preparation method and application thereof Download PDFInfo
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- 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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
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- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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
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- 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
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
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- 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
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
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- 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 invention relates to low-temperature-resistant fluoroether rubber and a preparation method and application thereof. The low-temperature-resistant fluoroether rubber is obtained by taking a first-class comonomer, a second-class comonomer and a low-temperature comonomer as comonomers, iodo perfluoroolefin as a vulcanization point monomer and iodo alkane as a chain transfer agent through emulsion polymerization; wherein the first comonomer is vinylidene fluoride; the second comonomer is perfluoropropylene and/or tetrafluoroethylene; the low-temperature comonomer is perfluoroalkyl vinyl ether. According to the invention, by optimizing various fluorine-containing olefins, vulcanization point monomers, emulsifiers, chain transfer agents, reaction pressure, temperature and other conditions, the obtained product has excellent processing performance, tensile strength, permanent compression deformation and other performances, and meanwhile, the low-temperature performance TR-10 is-30 to-37 ℃, and the low-temperature brittleness temperature is-45 to-50 ℃.
Description
Technical Field
The invention relates to low-temperature-resistant fluoroether rubber as well as a preparation method and application thereof, belonging to the technical field of fluorine chemical industry.
Background
Compared with common fluororubbers, the low-temperature-resistant fluororubber has better low-temperature flexibility and excellent physical properties and processability, and is widely applied to sealing of chemical reaction devices of various factories, chemical pipeline linings and fittings, sealing parts in the semiconductor industry, and special parts in the automobile industry, the petrochemical industry and the aerospace industry.
In the prior art, more reports about low-temperature resistant fluorine-containing elastomers and preparation methods thereof are published, such as taking vinylidene fluoride, tetrafluoroethylene and perfluoromethyl vinyl ether as comonomers and adopting CF2＝CFOCF2CF2CF2OCF2Br is a vulcanization point monomer, perfluorooctanoic acid is used as an emulsifier, diethyl malonate and the like are used as chain transfer agents. The obtained product has excellent low-temperature resistance, but is slightly insufficient in tensile strength, solvent resistance and other properties.
In addition, there is also a literature disclosing a process for the preparation of a special low temperature resistant fluororubber using vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and other optional comonomers selected from: one or more of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, vinyl fluoride, ethylene, propylene, trifluoroethylene, chlorotrifluoroethylene, difluorodichloroethylene, 3,3, 3-trifluoropropylene and perfluoroalkylethylene is/are used as a comonomer, special fluoroether carboxylate is used as a surfactant, and a radical initiator is used for copolymerization in a pressure-resistant reaction kettle. The low-temperature brittleness temperature of the obtained product is about-30 ℃, and the control difficulty of the polymerization condition is high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel low-temperature-resistant fluoroether rubber and a preparation method thereof. By optimizing the conditions of various fluorine-containing olefins, vulcanization point monomers, emulsifiers, chain transfer agents, reaction pressure, temperature and the like, the obtained product has excellent processing performance, tensile strength, permanent compression set and the like, and meanwhile, the low-temperature performance TR-10 is-30 to-37 ℃, and the low-temperature brittleness temperature is-45 to-50 ℃.
The technical scheme adopted by the invention is as follows.
A low-temperature-resistant fluoroether rubber is prepared by taking a first-class comonomer, a second-class comonomer and a low-temperature comonomer as comonomers, taking iodoperfluoroolefin (CSM) as a vulcanization point monomer, taking iodoalkane as a chain transfer agent and carrying out emulsion polymerization reaction under certain temperature and pressure conditions;
wherein the first comonomer is vinylidene fluoride (VDF);
the second comonomer is perfluoropropene (HFP) and/or Tetrafluoroethylene (TFE);
the low-temperature comonomer is perfluoroalkyl vinyl ether (PAVE).
Further, the perfluoroalkyl vinyl ether is preferably one or more of perfluoromethyl vinyl ether (PMVE), perfluoro-n-propyl vinyl ether (PPVE), perfluoroethyl vinyl ether (PEVE); PMVE is preferred.
Further, the mole ratio of the first comonomer, the second comonomer and the low-temperature comonomer is (60-85): (0-10): (15-40); preferably (60-70): (5-10): (20-30).
Further, the first type of comonomer, the second type of comonomer, and the low temperature comonomer are preferably one of the following combinations:
VDF/HFP/PMVE (molar ratio of 60-85: 0-10: 15-40)), VDF/HFP/PPVE (molar ratio of 60-70: 5-10: 20-30)), VDF/HFP/PEVE (molar ratio of 60-70: 5-10: 20-30)), (C/H/P) and (C/H/P) and (C/P) are mixed together to form the composite material,
VDF/TFE/PMVE (molar ratio (60-70): (3-8): 22-37)), VDF/TFE/PPVE (molar ratio (60-70): 3-8): 22-37)), VDF/TFE/PEVE (molar ratio (60-70): 3-8): 22-37), VDF/TFE/PMVE/PPVE (molar ratio (60-70): 3-8): 22-37) and the like.
Further, the usage amount of the vulcanization point monomer is 0.01-4.5% of the total mass of the low-temperature-resistant fluoroether rubber; preferably 0.4-4.0%.
Further, the sulfide site monomers include, but are not limited to, iodotrifluoroethylene, perfluoroiodoethyl vinyl ether, perfluoroiodoethoxy vinyl ether, perfluoroiodoethoxypropyl vinyl ether, perfluoroiodomethoxymethyl vinyl ether, perfluoroiodo-3, 5-dioxahexyl vinyl ether, and the like.
Further, the dosage of the chain transfer agent is 0.2-1.5% of the total mass of the low-temperature-resistant fluoroether rubber.
The chain transfer agent is α, omega-diiodoalkane, α, omega-diiodoperfluoroalkane, preferably one or more of diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodopentane, 1, 4-diiodoperfluorobutane, and the like, and more preferably 1, 4-diiodoperfluorobutane.
The invention also provides a preparation method of the low-temperature-resistant fluoroether rubber, which comprises the following steps: the emulsion polymerization is carried out under the conditions of certain temperature and pressure by taking a first comonomer, a second comonomer and a low-temperature comonomer as comonomers, taking iodo perfluoroolefin (CSM) as a vulcanization point monomer and iodo alkane as a chain transfer agent;
wherein the first comonomer is vinylidene fluoride (VDF);
the second comonomer is perfluoropropene (HFP) and/or Tetrafluoroethylene (TFE);
the low-temperature comonomer is perfluoroalkyl vinyl ether (PAVE);
the pressure is controlled between 0.5 and 4 MPa; preferably 1 to 3MPa, and further preferably 2 to 3 MPa;
the temperature is controlled to be between 60 and 95 ℃; preferably 60 to 90 ℃ and more preferably 80 ℃.
In order to obtain the low-temperature-resistant fluoroether rubber with more ideal performance, the invention strictly controls the polymerization pressure in the preparation process, and avoids the problems that the reaction cannot be carried out, or the product has overlarge molecular weight and high Mooney viscosity.
Further, the emulsifier used in the preparation method is a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1; the addition amount of the emulsifier is 0.05-0.2% of the total mass of the low-temperature-resistant fluoroether rubber.
The initiator used was ammonium persulfate. The addition amount of the initiator is 0.015-0.2% of the total mass of the low-temperature-resistant fluoroether rubber.
As one of preferred embodiments of the present invention, the method for preparing the low temperature resistant fluoroether rubber comprises:
(1) adding deionized water with the volume of 60-70% of the reaction kettle and a pH buffering agent into the reaction kettle, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 60-95 ℃;
(2) adding a comonomer into the reaction kettle until the pressure in the kettle reaches 0.5-4 MPa; continuously adding an emulsifier and a vulcanization point monomer, adding a free radical initiator and a chain transfer agent, simultaneously replenishing a comonomer after initiating a polymerization reaction, and maintaining the reaction pressure in the reaction kettle;
(3) stopping feeding when the accumulated feeding amount reaches 8-15 kg along with the reaction, and obtaining an elastomer emulsion after the reaction is finished;
(4) adding a coagulant into the elastomer emulsion, coagulating, washing, and drying in vacuum at 70-90 ℃ to obtain the low-temperature-resistant fluoroether rubber.
The invention also provides application of the low-temperature-resistant fluoroether rubber in sealing of chemical reaction devices in factories, linings and fittings of chemical pipelines, sealing parts in the semiconductor industry, or special part products in the automobile industry, the petrochemical industry and the aerospace industry.
The invention has the following beneficial effects:
the invention selects VDF, HFP and/or TFE and PAVE as main comonomers, and carries out emulsion polymerization in an emulsifier system with a vulcanization point monomer and a chain transfer agent under the action of an initiator to finally obtain the low-temperature-resistant fluoroether rubber. The glass transition temperature of the obtained product is-30 to-37 ℃, the low-temperature rebound temperature TR-10 of the vulcanized product is-30 to-37 ℃, the low-temperature brittleness temperature is-40 to-47 ℃, and the obtained low-temperature-resistant fluoroether rubber also has the properties of high strength, low permanent compression deformation 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.
In the following examples, the performance index detection methods were as follows:
1. glass transition temperature: DSC, taking the median value.
2. And (3) vulcanized product TR-10: GB/T7758-2002.
3. Low temperature brittleness temperature: GB/T15256-1994.
4. Tensile strength; GB/T528-2008.
5. Permanent compression set (O-ring, 232 ℃, 70 h): GB/T7759.0-2015.
EXAMPLE 1 preparation of Low temperature resistant fluoroether rubber
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 25g of emulsifier (a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 80 ℃;
(2) a mixed monomer of VDF/TFE/PMVE 70/10/20 (molar ratio) was introduced into a reactor by a compressor, the pressure was increased to 2.5MPa at 80 ℃, 350g of trifluoroiodoethylene was added, 100g of a 15 wt% aqueous ammonium persulfate solution was then introduced by a metering pump to initiate polymerization, and ICF was added when the pressure in the reactor was decreased to 2.4MPa2CF2125g, and simultaneously adding mixed monomers of VDF/TFE/PMVE (molar ratio) 70/10/20, and keeping the pressure in the reaction kettle at 2.5 MPa;
(3) with the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-31 ℃, the TR-10 of a vulcanized product is-32 ℃, and the low-temperature brittleness temperature is-40 ℃. Tensile strength 23.8MPa, permanent compression deformation (O-ring, 200 ℃, 70h) 13%.
Example 2 preparation of Low temperature resistant fluoroether rubber
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 25g of emulsifier (a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 90 ℃;
(2) adding mixed monomer with VDF/PMVE 60/40 (molar ratio) into a reaction kettle by a compressor, increasing the pressure to 1.5MPa at 90 ℃, adding 400g of perfluoro iodo ethoxy propyl vinyl ether, then pressing 120g of 15 percent (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization, adding ICF when the pressure of the reaction kettle is reduced to 1.45MPa, adding2CF2125g of monomer mixture (VDF/PMVE 60/40) was added to the reactor, and the pressure in the reactor was kept at 1.5 MPa.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-37 ℃, the TR-10 of a vulcanized product is-37 ℃, and the low-temperature brittleness temperature is-47 ℃. The tensile strength is 18.9MPa, and the permanent compression deformation (O-shaped ring, 200 ℃, 70h) is 20 percent.
EXAMPLE 3 preparation of Low temperature resistant fluoroether rubber
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 25g of emulsifier (a mixture of perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 60 ℃;
(2) adding mixed monomer with VDF/PMVE (molar ratio) of 85/15 into a reaction kettle by a compressor, boosting the temperature to 1.0MPa at 60 ℃, adding 10g of iodotrifluoroethylene, then pressing 90g of 15 percent (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization, adding 20g of diiodomethane when the pressure of the reaction kettle is reduced to 0.9MPa, simultaneously supplementing mixed monomer with VDF/PMVE (molar ratio) of 85/15, and keeping the pressure in the reaction kettle at 1.0 MPa.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-36 ℃, the TR-10 of a vulcanized product is-36 ℃, and the low-temperature brittleness temperature is-46 ℃. The tensile strength is 19.5MPa, and the permanent compression deformation (O-shaped ring, 200 ℃, 70h) is 23 percent.
Example 4 preparation of Low temperature resistant fluoroether rubber
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 20g of emulsifier (a 1:1 mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 80 ℃;
(2) charging VDF/HFP/PMVE 60/10/30 (molar ratio) mixed monomer into a reaction kettle by a compressor, increasing the pressure to 2.8MPa at 80 ℃, adding 40g of perfluoro iodo ethoxy propyl vinyl ether, then pressing 10g of 15% (wt) ammonium persulfate aqueous solution by a metering pump to initiate polymerization, and adding ICF when the pressure of the reaction kettle is reduced to 2.7MPa2CF2CF2CF2I24g, and simultaneously adding mixed monomers of VDF/HFP/PMVE 60/10/30 (molar ratio), and keeping the pressure in the reaction kettle at 2.8 MPa.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-33 ℃, the TR-10 of a vulcanized product is-33 ℃, and the low-temperature brittleness temperature is-41 ℃. The tensile strength is 20.5MPa, and the permanent compression deformation (O-shaped ring, 200 ℃, 70h) is 20 percent.
EXAMPLE 5 preparation of Low temperature resistant fluoroether rubber
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 20g of emulsifier (a 1:1 mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 80 ℃;
(2) a mixed monomer of VDF/HFP/PMVE 70/5/25 (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 ICF was added when the pressure in the reactor was decreased to 2.7MPa2CF2CF2CF2I25g was supplemented with mixed monomer of VDF/HFP/PMVE 70/5/25 (molar ratio) to maintain a pressure of 2.8MPa in the reactor.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-36 ℃, the TR-10 of a vulcanized product is-36 ℃, and the low-temperature brittleness temperature is-45 ℃. The tensile strength is 19.7MPa, and the permanent compression deformation (O-shaped ring, 200 ℃, 70h) is 21 percent.
Effect verification
Comparative example 1
The method does not use perfluoroalkyl vinyl ether (including perfluoro-n-propyl vinyl ether, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether) and the like, and only adopts tetrafluoroethylene, perfluoropropylene and vinylidene fluoride as comonomers.
(1) Adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 20g of emulsifier (a 1:1 mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 80 ℃;
(2) a mixed monomer of VDF/TFE/HFP 75/8/17 (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 introduced by a metering pump to initiate polymerization, and ICF was added when the pressure in the reactor was decreased to 2.7MPa2CF2CF2CF2While adding 25g of a monomer mixture of VDF/TFE/HFP (molar ratio) 75/8/17, the pressure in the reactor was kept at 2.8 MPa.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-22 ℃, the TR-10 of a vulcanized product is-22 ℃, and the low-temperature brittleness temperature is-35 ℃. Tensile strength 20.3MPa, permanent compression deformation (O-ring, 200 ℃, 70h) 25%.
Comparative example 2
The amount of perfluoromethyl vinyl ether used was reduced and the experiment was carried out according to the following procedure.
The method comprises the following steps:
(1) adding 30L of deionized water, 18g of dipotassium hydrogen phosphate and 20g of emulsifier (a mixture of ammonium perfluoropolyether carboxylate and sodium octyl sulfonate in a mass ratio of 1: 1) into a 50L stainless steel reaction kettle with a stirrer, repeatedly pressurizing with nitrogen, evacuating and degassing until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 80 ℃;
(2) a mixed monomer of VDF/HFP/PMVE 75/20/5 (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 ICF was added when the pressure in the reactor was decreased to 2.7MPa2CF2CF2CF2I25g was supplemented with mixed monomer of VDF/HFP/PMVE 75/20/5 (molar ratio) to maintain a pressure of 2.8MPa in the reactor.
(3) With the reaction, the material feeding amount reaches 10kg, and the reaction is stopped to obtain elastomer emulsion;
(4) and adding a magnesium chloride aqueous solution into the elastomer emulsion for coagulation, washing, and continuously drying in a vacuum drying oven at 80 ℃ for 8 hours to obtain the elastomer product low-temperature-resistant fluoroether rubber.
Through detection, the glass transition temperature of the obtained low-temperature-resistant fluoroether rubber is-26 ℃, the TR-10 of a vulcanized product is-26 ℃, and the low-temperature brittleness temperature is-35 ℃. Tensile strength 18.6MPa, permanent compression deformation (O-ring, 200 ℃, 70h) 27%.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may 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 low temperature resistant fluoroether rubber is characterized in that a first kind of comonomer, a second kind of comonomer and a low temperature comonomer are taken as comonomers, iodoperfluoroolefin is taken as a vulcanization point monomer, iodoalkane is taken as a chain transfer agent, and the low temperature resistant fluoroether rubber is obtained through emulsion polymerization;
wherein the first comonomer is vinylidene fluoride;
the second comonomer is perfluoropropylene and/or tetrafluoroethylene;
the low-temperature comonomer is perfluoroalkyl vinyl ether.
2. The low temperature resistant fluoroether rubber of claim 1, wherein the molar ratio of the first comonomer, the second comonomer and the low temperature comonomer is (60-85): (0-10): (15-40); preferably (60-70): (5-10): (20-30).
3. The low temperature resistant fluoroether rubber of claim 1 or 2, wherein the first type of comonomer, the second type of comonomer, the low temperature comonomer are selected from one of the following combinations:
VDF/HFP/PMVE、VDF/HFP/PPVE、VDF/HFP/PEVE、
VDF/TFE/PMVE、VDF/TFE/PPVE、VDF/TFE/PEVE、VDF/TFE/PMVE/PPVE。
4. the low temperature resistant fluoroether rubber according to any one of claims 1 to 3, wherein the amount of the vulcanization point monomer is 0.01 to 4.5% of the total mass of the low temperature resistant fluoroether rubber; preferably 0.4-4.0%;
and/or the presence of a gas in the gas,
the said sulfuration point monomer is selected from one or more of iodo trifluoroethylene, perfluoro iodo ethyl vinyl ether, perfluoro iodo ethoxy propyl vinyl ether, perfluoro iodo methoxy methyl vinyl ether, and perfluoro iodo-3, 5-dioxahexyl vinyl ether.
5. The low temperature resistant fluoroether rubber of any one of claims 1 to 4, wherein said chain transfer agents are α, ω -diiodo alkane and α, ω -diiodo perfluoroalkane;
preferably one or more of diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodopentane and 1, 4-diiodoperfluorobutane;
further preferred is 1, 4-diiodoperfluorobutane.
6. The low temperature resistant fluoroether rubber according to any one of claims 1 to 5, wherein in the polymerization process of the low temperature resistant fluoroether rubber, the used emulsifier is prepared by mixing perfluoropolyether peroxide and sodium octyl sulfonate in a mass ratio of 1: 1; the addition amount of the emulsifier is 0.05-0.2% of the total mass of the low-temperature-resistant fluoroether rubber.
7. A preparation method of low temperature resistant fluoroether rubber is characterized by comprising the following steps: the emulsion polymerization is carried out under certain temperature and pressure conditions by taking a first comonomer, a second comonomer and a low-temperature comonomer as comonomers, taking iodo perfluoroolefin as a vulcanization point monomer and iodo alkane as a chain transfer agent;
wherein the first comonomer is vinylidene fluoride;
the second comonomer is perfluoropropylene and/or tetrafluoroethylene;
the low-temperature comonomer is perfluoroalkyl vinyl ether;
the pressure is controlled between 0.5 and 4 MPa;
the temperature is controlled to be between 60 and 95 ℃.
8. The method according to claim 7, wherein the pressure is 1-3MPa, preferably 2-3 MPa;
and/or the temperature is 60 to 90 ℃, preferably 80 ℃.
9. The method of claim 7, comprising:
(1) adding deionized water with the volume of 60-70% of the reaction kettle and a pH buffering agent into the reaction kettle, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 60-95 ℃;
(2) adding a comonomer into the reaction kettle until the pressure in the kettle reaches 0.5-4 MPa; continuously adding an emulsifier and a vulcanization point monomer, adding a free radical initiator and a chain transfer agent, simultaneously replenishing a comonomer after initiating a polymerization reaction, and maintaining the reaction pressure in the reaction kettle;
(3) stopping feeding when the accumulated feeding amount reaches 8-15 kg along with the reaction, and obtaining an elastomer emulsion after the reaction is finished;
(4) adding a coagulant into the elastomer emulsion, coagulating, washing, and drying in vacuum at 70-90 ℃ to obtain the low-temperature-resistant fluoroether rubber.
10. Use of the low temperature resistant fluoroether rubber of any one of claims 1 to 6 in seals for chemical reaction devices, chemical line linings and fittings, seals in the semiconductor industry, or specialty parts in the automotive, petrochemical and aerospace industries.
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