CN110684141A - Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content - Google Patents
Peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content Download PDFInfo
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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
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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- 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
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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
- C08F214/28—Hexyfluoropropene
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Abstract
The invention relates to peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content, which is prepared by emulsion polymerization reaction at certain temperature and pressure conditions by using vinylidene fluoride, tetrafluoroethylene and perfluoropropylene as main comonomers, halogenated perfluoroolefin as a vulcanization point monomer and iodoalkane as a chain transfer agent, wherein the fluorine content is more than or equal to 69 percent, and the Mooney viscosity is 2-35. The product has the advantages of good fluidity, excellent performance of being used for extrusion, injection processing and molding, methanol resistance and other media, and good mechanical performance.
Description
Technical Field
The invention relates to peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content, belonging to the technical field of fluorine chemical industry.
Background
Fluororubbers (FKM) are synthetic polymer elastomers having fluorine atoms attached to carbon atoms of the main or side chains of the molecule. Fluororubbers were first tried in 1948 by DuPont in the United states to produce poly-2-fluoro-1.3-butadiene and its copolymers with styrene, propylene, etc., but their properties are not better than those of chloroprene rubber and butadiene rubber, and they are expensive and have no practical industrial value. In the later 50 s, Thiokol corporation developed a binary nitroso-fluoro rubber with good low temperature and strong oxidation resistance (N2O4), and the fluoro rubber began to enter into practical industrial application. Since then, with the progress of technology, various novel fluororubbers have been developed. The high bond energy and the unique bond length structure of the C-F bond endow the material with a series of excellent performances such as high temperature resistance, chemical medium resistance, flame retardance, aging resistance and the like, become irreplaceable key materials in modern industry, particularly in the high-technology field, and are widely applied to the fields of aerospace, vehicles and ships, electronic communication, petrochemical industry and the like.
In recent years, with the expansion of fluororubber application, the demand on fluororubber is increasing, and the existing fluororubber grade can not meet the market demand more and more, which stimulates the application market of special fluororubber. Under the condition of increasingly tense energy, the emergence of novel environment-friendly energy and fuel requires that the fluororubber has excellent solvent resistance. With the increase of the fluorine content, the volume change rate of the fluororubber in methanol is small, and the oil resistance and the solvent resistance are improved. Although the prior fluororubbers have more varieties, the fluororubbers belong to the conventional fluoroelastomer, and the bisphenol with high fluororubber content, which can meet the application requirements on oil resistance and solvent resistance, has poor vulcanization effect and even can not be vulcanized.
The high-fluorine-containing rubber mainly comprises rubber seeds with medium and high Mooney viscosity, is basically processed by die pressing, and has unstable product quality and low production efficiency. The low-Mooney viscosity fluororubber adopts the processing method of extrusion and injection molding, and can make up for the deficiency of the mechanical property by improving the formula. The low Mooney viscosity rubber has the characteristics of moderate vulcanization speed, good elasticity, easy processing, good demolding property and the like, can meet the requirement of processing products with complex geometric shapes, has stable product performance and high production efficiency, and is the mainstream direction for developing and processing fluororubber.
ZL200610169796.9 discloses a fluoroelastomer with high fluorine content and a preparation method thereof, wherein the fluorine content is more than 70%. The method takes water as a medium, low molecular lipids as a chain transfer agent, persulfate as an initiator, perfluorooctanoate as a dispersing agent and borax as a pH regulator, and the elastomer with high fluorine content is obtained by an emulsion polymerization mode, and has excellent methanol resistance and fuel oil resistance. However, the fluororubber synthesized by the method has high Mooney viscosity, and the low Mooney fluororubber has poor vulcanization effect by adopting a bisphenol mode, and the vulcanized test piece is easy to generate bubbles.
The patent ZL201410331103.6 discloses a low-Mooney viscosity high-fluorine-content fluororubber and a preparation method thereof, wherein vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene are used as comonomers and are polymerized by emulsion, the Mooney viscosity of a product is 18-30 (ML1 ═ 10min @121 ℃), the product is vulcanized by a bisphenol system, and the vulcanized product has poor properties such as tensile strength, elongation and methanol resistance.
Disclosure of Invention
The invention provides peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content and a preparation method thereof. The Mooney viscosity of the fluororubber product is 2-35 (ML 1-10 min @121 ℃), the fluorine content of the fluororubber product is more than or equal to 69%, and the fluororubber product has the advantages of good fluidity, excellent performances of methanol and other media resistance and good mechanical properties, and can be used for extrusion and injection molding.
In order to achieve the purpose, the invention adopts the following technical scheme:
a peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content is prepared by emulsion polymerization reaction under certain temperature and pressure conditions by using vinylidene fluoride (VDF), Tetrafluoroethylene (TFE) and perfluoropropylene (HFP) as main comonomers, using halogenated perfluoroolefin as a vulcanization point monomer and using iodoalkane as a chain transfer agent.
Wherein the molar ratio of vinylidene fluoride (VDF), Tetrafluoroethylene (TFE) and perfluoropropylene (HFP) in the comonomer is (65-30): (15-20): (20-50), and preferably 60:20: 20.
In one embodiment of the invention, the comonomer has a molar ratio of vinylidene fluoride (VDF), Tetrafluoroethylene (TFE), and perfluoropropylene (HFP) of 65:15: 20.
In one embodiment of the invention, the molar ratio of vinylidene fluoride (VDF), Tetrafluoroethylene (TFE), and perfluoropropylene (HFP) in the comonomer is 30:20: 50.
Further, the vulcanization point monomer is halogenated perfluoroolefin, and specifically can be one or more of trifluorobromoethylene, trifluoroiodoethylene, perfluoroiodoalkyl vinyl ether, perfluorobromoalkyl vinyl ether, vinyl bromide, vinylidene fluoride, 3,4, 4-tetrafluoro-4-iodobut-1-ene and the like; preferably a perfluoroiodoalkyl vinyl ether.
Further, the iodo-alkyl vinyl ether includes, but is not limited to, one or more of perfluoro-iodo-ethyl vinyl ether, perfluoro-iodo-ethoxy vinyl ether, perfluoro-iodo-ethoxypropyl vinyl ether, perfluoro-iodo-methoxymethyl vinyl ether, perfluoro-iodo-3, 5-dioxahexyl vinyl ether, and the like.
Further, the dosage of the halogenated perfluoroolefin of the vulcanization point monomer is 0.1-4% (mass fraction) of the dosage of the comonomer.
Further, the chain transfer agent is an alkyl iodide, and specifically may be selected from α, ω -diiodoalkane or α, ω -diiodoperfluoroalkane, such as diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodoperfluoropentane, 1, 4-diiodoperfluorobutane, and the like. 1, 4-diiodoperfluorobutane is preferred.
Further, the dosage of the chain transfer agent iodoalkane is 0.06% -6% of the monomer dosage.
Further, the polymerization reaction pressure is 1-5MPa, and preferably 2-4 MPa.
In order to ensure that the low Mooney viscosity of the fluororubber meets the requirement, the invention optimally selects the reaction pressure. The polymerization pressure is too low, the reaction cannot be carried out, the molecular weight of the product obtained by the too high polymerization pressure is large, and the Mooney viscosity is high. Researches show that the effect is better when the reaction pressure is 1-5 MPa.
Further, the polymerization reaction temperature is 60-100 ℃, and the preferable polymerization reaction temperature is 70-95 ℃.
The invention also provides a preparation method of the peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content, which comprises the following steps:
1) adding deionized water (generally, the added water accounts for 60-70% of the volume 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 kettle to 60-100 ℃;
2) adding the above comonomer (mainly VDF/TFE/HFP) into the reaction kettle until the pressure in the kettle reaches 1-5 MPa; adding an emulsifier and a vulcanization point monomer, and adding a free radical initiator and a chain transfer agent to initiate polymerization; the comonomer is added into the reaction kettle at any time in the reaction process so as to maintain the pressure in the kettle (within the polymerization pressure range of 1-5 MPa);
3) stopping feeding when the accumulated material feeding amount reaches the target mass along with the reaction, and finishing the reaction (generally taking a 50L reaction kettle as an example, the target mass is that the accumulated material feeding amount reaches 8-15 kg);
4) and (3) coagulating, washing and drying the elastomer emulsion obtained by the reaction, or further plasticating and molding by a rubber mixing machine to obtain the peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content.
Further, the dosage of the chain transfer agent is 0.06% -6% of the dosage of the monomer.
Further, the pH buffering agent is selected from one or more of phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate and the like; preferably dipotassium hydrogen phosphate or sodium bicarbonate.
Further, the emulsifier comprises a salt of a perfluorocarboxylic acid, a salt of a perfluoropolyether carboxylic acid, preferably a salt of a perfluoropolyether carboxylic acid.
Further, the free radical initiator is water-soluble inorganic peroxide, preferably ammonium persulfate or potassium persulfate or a mixture of the ammonium persulfate and the potassium persulfate.
The present invention can control the polymerization rate by controlling the polymerization temperature, the reaction pressure, and by the amount of the initiator and the amount of the chain transfer agent added, and the polymerization time is usually 1 to 10 hours.
Further, the polymerization reaction temperature is 60-100 ℃, and the preferable polymerization reaction temperature is 70-95 ℃.
The coagulation, washing and drying of the elastomer emulsions described herein are carried out using processes conventional in the art. Generally, drying can be carried out at 70-90 ℃ for 10-18h under vacuum.
The invention also comprises the peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content prepared by the method.
According to the invention, VDF/TFE/HFP main comonomer, a vulcanization point monomer and a chain transfer agent are subjected to emulsion polymerization in an emulsifier system under the action of an initiator to finally obtain the fluororubber, wherein the fluorine content is not less than 69%, and the Mooney viscosity of the product is 2-35 (ML1 ═ 10min @121 ℃). Has excellent flowability and may be produced through extrusion and injection molding. The vulcanized product has excellent mechanical performance and methanol resistance.
The peroxide-vulcanized fluororubbers having a low Mooney viscosity and a high fluorine content, which are produced by the above-mentioned method, are required to be molded and vulcanized during the production thereof into products such as automobile lubricating oil pipes or sealing tapes, etc., and general vulcanization methods use polyols, polyamines, or add an organic peroxide vulcanizing agent.
The starting materials used in the present invention are commercially available or may be prepared by methods conventional in the art.
On the basis of the common knowledge in the field, the above preferred conditions can be combined with each other to obtain the preferred embodiments of the invention.
The product obtained by the invention can be cross-linked and vulcanized by adopting a peroxide vulcanization system, and the vulcanized product has the characteristics of high strength, drug (acid and alkali) resistance, water vapor resistance, ozone resistance, high temperature resistance, alcohol solvent resistance and the like, can be used for preparing products such as diaphragms, fuel pipes, oil tank sealing gaskets, oxygen sensing sealing parts, sealing rings and the like, and is applied to more severe environments (such as water vapor, ozone, alkaline environments, methanol and the like) compared with common bisphenol vulcanized fluororubber. Therefore, the peroxide vulcanized fluororubber is mostly used in aerospace, petroleum and automobile industries as a framework oil seal, an extrusion molding product, a gasket, an O-shaped ring and the like, and is increasingly widely applied in the automobile field especially under the background of large-scale popularization and application of various novel environment-friendly alcohol-containing fuels at present.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Mooney ML1 ═ 10min @121 ℃ test according to ATSM D1646.
The following vulcanizing agent formula is used: 4 parts of 2, 5-dimethyl-2, 5-dihexyl (dipenta, 75%), 3 parts of triallyl isocyanurate (TAIC) and 20 parts of N990 carbon black. Generally, 27 parts of the above vulcanizing agent are used per 100 parts of raw rubber.
One-stage vulcanization is carried out at 170 ℃ for 10min, and two-stage vulcanization is carried out at 232 ℃ for 4 h.
Tensile strength test method is according to ASTM D412.
Elongation test method was according to ASTM D412.
Hardness test method is according to ASTM D2240.
Permanent compression set test method is according to ASTM D1414.
Post-aging strength test method was according to ASTM D412.
Volume rate of change test method was according to ASTM D471.
Example 1
In this example, VDF: TFE: HFP is 65:15:20 (molar ratio).
Adding 30L of deionized water, 60g of dipotassium hydrogen phosphate and 30g of emulsifier into a 50L stainless steel reaction kettle with a stirrer, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 80 ℃;
adding VDF/TFE/HFP three main comonomers into a reaction kettle until the pressure in the kettle reaches 4.0 MPa; 400g of 3,3,4, 4-tetrafluoro-4-iodobut-1-ene is added, 10g of potassium persulfate serving as an initiator and 800g of 1, 4-diiodoperfluorobutane serving as a chain transfer agent are added, the reaction is started, and the VDF/TFE/HFP three main comonomers are added to ensure that the reaction pressure of the reaction kettle is within the range of 4.0 +/-0.1 MPa.
Stopping feeding when the accumulated feeding amount reaches 15kg along with the reaction, and finishing the reaction; obtaining fluororubber emulsion, coagulating with magnesium chloride aqueous solution, washing with deionized water, and continuously drying in a vacuum drying oven at 90 deg.C and-0.09 MPa for 14h to obtain rubber product.
The Mooney viscosity of the raw rubber product is 4(ML1 ═ 10min @121 ℃), and the fluorine content: 69.0 percent. The following formulation was used for vulcanization:
the results obtained were as follows:
example 2
In this example, VDF: TFE: HFP is 60:20:20 (molar ratio).
Adding 30L of deionized water, 60g of dipotassium hydrogen phosphate and 30g of emulsifier into a 50L stainless steel reaction kettle with a stirrer, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 80 ℃;
adding VDF/TFE/HFP three main comonomers into a reaction kettle until the pressure in the kettle reaches 4.0 MPa; 400g of 3,3,4, 4-tetrafluoro-4-iodobut-1-ene is added, 10g of potassium persulfate serving as an initiator and 700g of 1, 4-diiodoperfluorobutane serving as a chain transfer agent are added, the reaction is started, and the VDF/TFE/HFP three main comonomers are added to ensure that the reaction pressure of the reaction kettle is within the range of 4.0 +/-0.1 MPa.
Stopping feeding when the accumulated feeding amount reaches 15kg along with the reaction, and finishing the reaction; obtaining fluororubber emulsion, coagulating with magnesium chloride aqueous solution, washing with deionized water, and continuously drying in a vacuum drying oven at 90 deg.C and-0.09 MPa for 14h to obtain rubber product.
The Mooney viscosity of the product was 6(ML1 ═ 10min @121 ℃ C.), and the fluorine content: 69.2 percent. The product was vulcanized in the same manner as in example 1.
The results obtained were as follows:
example 3
In this example, VDF: TFE: HFP is 30:20:50 (molar ratio).
Adding 30L of deionized water, 60g of dipotassium hydrogen phosphate and 30g of emulsifier into a 50L stainless steel reaction kettle with a stirrer, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 80 ℃;
adding VDF/TFE/HFP three main comonomers into a reaction kettle until the pressure in the kettle reaches 4.5 MPa; 400g of 3,3,4, 4-tetrafluoro-4-iodobut-1-ene is added, 15g of potassium persulfate serving as an initiator and 200g of 1, 4-diiodoperfluorobutane serving as a chain transfer agent are added, the reaction is started, and the VDF/TFE/HFP three main comonomers are added to ensure that the reaction pressure of the reaction kettle is within the range of 4.5 +/-0.1 MPa.
Stopping feeding when the accumulated feeding amount reaches 15kg along with the reaction, and finishing the reaction; obtaining fluororubber emulsion, coagulating with magnesium chloride aqueous solution, washing with deionized water, and continuously drying in a vacuum drying oven at 90 deg.C and-0.09 MPa for 14h to obtain rubber product.
The Mooney viscosity of the product was 20(ML1 ═ 10min @121 ℃ C.), and the fluorine content: 73 percent. The product was vulcanized in the same manner as in example 1.
The results obtained were as follows:
the vulcanization process used in the following examples is the same as in example 1.
Examples 4 to 11
The fluororubbers were prepared according to the following formulation according to the synthesis conditions and procedures of example 3.
The green rubber test results obtained for examples 4-11 are as follows:
test results after vulcanization of the raw rubbers obtained in examples 4 to 11
Example 12
In this example, VDF: TFE: HFP is 60:20:20 (molar ratio).
Adding 30L of deionized water, 60g of dipotassium hydrogen phosphate and 30g of emulsifier into a 50L stainless steel reaction kettle with a stirrer, vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the reaction kettle to 70 ℃;
adding VDF/TFE/HFP three main comonomers into a reaction kettle until the pressure in the kettle reaches 1.5 MPa; 400g of trifluoroiodoethylene is added, 25g of potassium persulfate serving as an initiator and 200g of 1, 4-diiodoperfluorobutane serving as a chain transfer agent are added, the reaction is started, and the VDF/TFE/HFP three main comonomers are added to ensure that the reaction pressure of the reaction kettle is within the range of 1.5 +/-0.1 MPa.
Stopping feeding when the accumulated feeding amount reaches 15kg along with the reaction, and finishing the reaction; obtaining fluororubber emulsion, coagulating with magnesium chloride aqueous solution, washing with deionized water, and continuously drying in a vacuum drying oven at 90 deg.C and-0.09 MPa for 14h to obtain rubber product.
The Mooney viscosity of the product was 26(ML1 ═ 10min @121 ℃ C.), and the fluorine content: 69.2 percent. The product was vulcanized in the same manner as in example 1.
The results obtained were as follows:
examples 13 to 16
Fluororubbers were prepared by following the procedure and formulation of example 2, with the following table only, changing the production temperature, reaction pressure and amount of potassium persulfate.
The results of the green rubber tests obtained in examples 13-16 are as follows:
| examples | Mooney ML1 ═ 10min @121 deg.C | Fluorine content% |
| 13 | 25 | 70 |
| 14 | 12 | 70 |
| 15 | 30 | 70 |
| 16 | 35 | 70 |
Examples 13-16 post cure rubber test results
Comparative example 1
30L of deionized water, 450g of ammonium perfluorooctanoate aqueous solution with the concentration of 50g/L and 80g of disodium hydrogen phosphate as a pH regulator are added into a 50L high-pressure reaction kettle, air in a vapor space in the reaction kettle is replaced by nitrogen and then by a mixed monomer to ensure that the oxygen content is less than 20ppm, and the reaction kettle is heated to 85 ℃. The initially mixed monomers (vinylidene fluoride: hexafluoropropylene: tetrafluoroethylene ═ 20: 58: 22, mol%) were charged into a reaction vessel by a diaphragm compressor to raise the pressure to 4.0 Mpa. When the pressure in the reaction kettle reached 4.0MPa, the stirring was started, the mixed monomers in the reaction kettle were thoroughly mixed, and then 160g of an initiator solution (50g/L, potassium persulfate) was added to start the reaction. During the reaction, the pressure of the reactor was maintained at 4.0MPa and the temperature was 85 ℃ by adding a mixed monomer (vinylidene fluoride: hexafluoropropylene: tetrafluoroethylene: trifluoropropene: 29: 33: 33: 5, mol%). 100g of methanol as a chain transfer agent was added. The reaction was terminated when the charge amount reached 12kg (cf. ZL 201410331103.6).
The properties of the obtained crude rubber are as follows:
| mooney ML1 ═ 10min @121 deg.C | Fluorine content% | |
| Comparative example 1 | 35 | 69 |
Secondly, the raw rubber obtained in the comparative example 1 is vulcanized by adopting the following peroxide vulcanization system:
| raw rubber | 100 portions of |
| ShuangErwu, 75% | 4 |
| TAIC | 3 |
| N990 | 20 |
| One stage vulcanization | 170℃×10min |
| Two stage vulcanization | 232℃×4h |
The vulcanizate properties were as follows:
and thirdly, vulcanizing the raw rubber obtained in the comparative example 1 by adopting the bisphenol vulcanization system as follows:
the properties of the product after bisphenol vulcanization are as follows:
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 peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content is characterized in that the peroxide vulcanized fluororubber is prepared by emulsion polymerization reaction under certain temperature and pressure conditions by using vinylidene fluoride, tetrafluoroethylene and perfluoropropylene as main comonomers, using halogenated perfluoroolefin as a vulcanization point monomer and using iodoalkane as a chain transfer agent;
wherein the molar ratio of vinylidene fluoride, tetrafluoroethylene and perfluoropropylene in the comonomer is (65-30): 15-20): 20-50.
2. The low-mooney high-fluorine peroxide-cured fluororubber according to claim 1, characterized in that the molar ratio of vinylidene fluoride, tetrafluoroethylene, perfluoropropylene in the comonomer is 60:20:20, 65:15:20 or 30:20: 50.
3. The low mooney viscosity high fluorine content peroxide vulcanized fluororubber according to claim 1 or 2, characterized in that the halogenated perfluoroolefin is selected from one or more of trifluorobromoethylene, trifluoroiodoethylene, perfluoroiodoalkyl vinyl ether, perfluorobromoalkyl vinyl ether, vinyl bromide, vinylidene fluoride, 3,4, 4-tetrafluoro-4-iodobut-1-ene; preferably a perfluoroiodoalkyl vinyl ether;
further preferably, the iodo-alkyl vinyl ether includes but is not limited to one or more of 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; and/or the presence of a gas in the gas,
preferably, the amount of the halogenated perfluoroolefin is 0.1 to 4 percent of the amount of the comonomer.
4. The low mooney viscosity high fluorine content peroxide vulcanized fluororubber according to any one of claims 1 to 3, characterized in that the alkyl iodide is an α, ω -diiodoalkane or an α, ω -diiodoperfluoroalkane; preferably diiodomethane, 1, 4-diiodobutane, 1, 3-diiodopropane, 1, 5-diiodoperfluoropentane, 1, 4-diiodoperfluorobutane; and/or the presence of a gas in the gas,
the dosage of the chain transfer agent iodoalkane is 0.06% -6% of the dosage of the monomer.
5. The low-Mooney high-fluorine peroxide-vulcanized fluororubber according to any one of claims 1 to 4, wherein the polymerization pressure is 1 to 5MPa, preferably 2 to 4 MPa; and/or the polymerization reaction temperature is 60-100 ℃, and the preferable polymerization reaction temperature is 70-95 ℃.
6. The low-Mooney high-fluorine peroxide-vulcanized fluororubber according to any one of claims 1 to 5, wherein the fluororubber has a fluorine content of not less than 69% and a Mooney viscosity of 2 to 35.
7. A process for producing a low-Mooney high-fluorine peroxide-vulcanized fluororubber according to any one of claims 1 to 6, characterized by comprising the steps of:
1) adding deionized water and a pH buffering agent into a reaction kettle; vacuumizing the reaction kettle until the oxygen content is less than or equal to 30ppm, and raising the temperature in the kettle to 60-100 ℃;
2) adding a comonomer into the reaction kettle until the pressure in the kettle reaches 1-5 MPa; adding an emulsifier and a vulcanization point monomer, and adding a free radical initiator and a chain transfer agent to initiate polymerization; the comonomer is added into the reaction kettle at any time in the reaction process so as to maintain the pressure in the kettle;
3) along with the reaction, stopping feeding when the accumulated material feeding amount reaches the target quality, and finishing the reaction;
4) and (3) coagulating, washing and drying the elastomer emulsion obtained by the reaction, or further plasticating and molding by a rubber mixing machine to obtain the peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content.
8. The preparation method according to claim 7, wherein the pH buffer is selected from one or more of phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate and hydrogen carbonate, preferably dipotassium hydrogen phosphate or sodium hydrogen carbonate; and/or the presence of a gas in the gas,
the emulsifier is selected from perfluorocarboxylates or perfluoropolyether carboxylates; and/or the presence of a gas in the gas,
the free radical initiator comprises water-soluble inorganic peroxide, preferably ammonium persulfate or potassium persulfate or a mixture of the ammonium persulfate and the potassium persulfate; and/or the presence of a gas in the gas,
the polymerization reaction temperature is 60-100 ℃, and the preferable polymerization reaction temperature is 70-95 ℃; and/or the polymerization time is 1 to 10 hours.
9. A low mooney viscosity high fluorine content peroxide-cured fluoroelastomer produced by the process of claim 7 or 8; preferably, the fluorine content of the fluororubber is not less than 69%, and the Mooney viscosity is 2-35.
10. A peroxide vulcanized fluororubber with low Mooney viscosity and high fluorine content is characterized in that the peroxide vulcanized fluororubber is prepared by emulsion polymerization reaction under certain temperature and pressure conditions by using vinylidene fluoride, tetrafluoroethylene and perfluoropropylene as main comonomers, using halogenated perfluoroolefin as a vulcanization point monomer and using iodoalkane as a chain transfer agent; the fluorine content of the fluororubber is more than or equal to 69%, and the Mooney viscosity is 2-35.
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| 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 |
| CN111849092A (en) * | 2020-08-26 | 2020-10-30 | 青岛科技大学 | High-strength high-hardness high-temperature-resistant fluororubber material and preparation method thereof |
| CN113461852A (en) * | 2020-03-30 | 2021-10-01 | 中昊晨光化工研究院有限公司 | Peroxide vulcanized fluororubber and preparation method thereof |
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| CN113461852A (en) * | 2020-03-30 | 2021-10-01 | 中昊晨光化工研究院有限公司 | Peroxide vulcanized fluororubber 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 |
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| CN115703860A (en) * | 2021-08-05 | 2023-02-17 | 中昊晨光化工研究院有限公司 | Tetrafluoroethylene modified peroxide vulcanized binary fluorine rubber and preparation method thereof |
| CN115703861A (en) * | 2021-08-05 | 2023-02-17 | 中昊晨光化工研究院有限公司 | Chlorotrifluoroethylene modified peroxide vulcanized fluororubber and preparation method thereof |
| CN115703861B (en) * | 2021-08-05 | 2024-04-02 | 中昊晨光化工研究院有限公司 | Trifluoro chloroethylene modified peroxide vulcanized fluororubber and preparation method thereof |
| CN115703860B (en) * | 2021-08-05 | 2024-04-02 | 中昊晨光化工研究院有限公司 | Tetrafluoroethylene modified peroxide vulcanized binary fluororubber and preparation method thereof |
| CN116143967A (en) * | 2021-11-22 | 2023-05-23 | 中昊晨光化工研究院有限公司 | Fluoroelastomer for lithium battery sealing and preparation method thereof |
| CN116143967B (en) * | 2021-11-22 | 2024-05-14 | 中昊晨光化工研究院有限公司 | Fluoroelastomer for lithium battery sealing and preparation method thereof |
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