CN109762091B - Tetrafluoroethylene-based copolymer and process for producing the same - Google Patents
Tetrafluoroethylene-based copolymer and process for producing the same Download PDFInfo
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Abstract
The invention belongs to the field of fluorine-containing high polymer materials, and particularly relates to a tetrafluoroethylene-based copolymer and a preparation method thereof. The tetrafluoroethylene-based copolymer is a copolymer comprising90 to 98 wt% of tetrafluoroethylene, 1 to 7 wt% of perfluoro-n-propyl vinyl ether and 1 to 3 wt% of a polymer having CF2＝CFCF2[OCF2CF(CF3)]nORfTerpolymer of structural perfluorpropenyl alkoxy ether or hydrogen-containing derivative thereof, wherein n is an integer of 0-5, RfIs a perfluoroalkyl group having 1 to 5 carbon atoms or a derivative containing a hydrogen atom; the tetrafluoroethylene-based copolymer has good melt fluidity and thermal stability, strong flexibility, high transparency and high surface smoothness; the preparation method adopts the environment-friendly solvent, avoids the damage to the atmospheric ozone layer, and is energy-saving and environment-friendly.
Description
Technical Field
The invention belongs to the field of fluorine-containing high polymer materials, and particularly relates to a tetrafluoroethylene-based copolymer and a preparation method thereof.
Background
Fusible polytetrafluoroethylene was first disclosed in 1972 in US patent No. US3635926 and is sold under the trade name Teflon PFA. The polytetrafluoroethylene is a copolymer of tetrafluoroethylene and a small amount of perfluoropropyl vinyl ether, and the main chain structure of the copolymer endows the copolymer with performances very similar to those of the polytetrafluoroethylene, and has excellent chemical stability, physical and mechanical properties, electrical insulation performance, lubricity, non-adhesiveness, aging resistance, non-combustibility and thermal stability. Because the main chain contains the perfluoroalkoxy side group, the flexibility of the chain is increased, and the melt viscosity of the polymer is improved, so that the polymer can be thermally processed by using a common processing technology.
Meltable polytetrafluoroethylene has many applications in the engineering field, and early meltable polytetrafluoroethylene resin is applied to reaction vessels such as beakers and flasks, reaction kettles, rectifying towers, storage tanks, pipelines, pipe fittings, hoses and the like for experiments in the chemical industry. With the development of industry, the application range is wider nowadays, and the film can be used as elements in the semiconductor manufacturing process, electronic element release films, equipment protective films, insulating layers of heating wires and special wires, and the like.
The prior art documents describe in more detail the polymerization of meltable polytetrafluoroethylene, but mainly binary copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether, and few patent documents report that the improvement of one or more specific properties of meltable polytetrafluoroethylene by modifying the meltable polytetrafluoroethylene with a third monomer during the polymerization reaction.
Japanese dajin in patents JP2003246823A and JP2007197561A discloses a terpolymer comprising tetrafluoroethylene, PVE and perfluoroethyl vinyl ether (PEVE) which exhibits excellent transparency and strength at normal and higher temperatures, but the side chain of the comonomer is relatively short, flexibility is poor, and improvement in flexibility is not significant over meltable polytetrafluoroethylene resin products prepared from conventional two-membered monomers.
Dajin in U.S. Pat. No. 4499249 discloses a process for the preparation of a terpolymer of tetrafluoroethylene and a perfluoroalkyl vinyl ether. The process employs suspension polymerization to
As an initiator, the perfluoroalkyl vinyl ether has the following structural formula:
wherein X is an F atom or an H atom, a is an integer of 0 to 4, and b is an integer of 0 to 7, and typical examples thereof are PMVE, PEVE and PPVE. The tetrafluoroethylene and perfluoroalkyl vinyl ether copolymer prepared by the method has lower unstable end group content and excellent folding endurance. But the initiating efficiency of the initiator used for polymerization is high, the addition amount of the initiator needs to be accurately controlled for polymerization, and the melt index is sensitive to the change of the addition amount of the initiator.
The 3M company disclosed a CF in US patent US20040024155A12＝CFO(CF2)nORfA structural monomer, wherein n is an integer of 2 to 6, and f is a perfluoroalkyl group having 1 to 6 carbon atoms. The use of tetrafluoroethylene with a small amount of CF in this patent2＝CFO(CF2)nORfThe derivative units of the structural monomers are copolymerized, and then the conventional olefin monomers such as hexafluoropropylene are properly added, and the side chains of the comonomers are long linear flexible chains, so that the bending fatigue strength, flexibility, light transmittance, chemical and thermal stress cracking performance of the product are obviously improved. The disadvantages are that the product has low melting pointThe melting point is 160 ℃ lower limit, and the thermal stability is relatively poor.
DuPont, in U.S. Pat. No. 5,983, 0161873A1, discloses a process for blending PTFE with a copolymer of tetrafluoroethylene and a perfluoroalkyl vinyl ether having the same structural formula as above formula (1). The blend prepared by the method has excellent chemical permeation resistance and good durability, can be used for injection molding of parts with complex shapes, has a melt index of more than 12g/10min, a folding endurance of more than 20000 cycles, and a nitrogen permeation coefficient of less than 0.8 x 10-10cm3(STP).cm/cm2Sec. The disadvantage is that the ratio of PTFE to PFA needs to be precisely controlled during mixing, and if PTFE is not uniformly mixed in the composition, the durability of the composition is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a tetrafluoroethylene-based copolymer which has good melt flowability and thermal stability, strong flexibility, high transparency and high surface smoothness; meanwhile, the invention also provides a preparation method of the composite material, which is scientific, reasonable, energy-saving and environment-friendly.
The tetrafluoroethylene-based copolymer is a terpolymer containing 90-98 wt% of tetrafluoroethylene, 1-7 wt% of perfluoro-n-propyl vinyl ether (PPVE) and 1-3 wt% of perfluoro-propenyl alkoxy ether or a hydrogen-containing derivative thereof;
the perfluoropropenyl alkoxy ether or its hydrogen-containing derivative has CF2＝CFCF2[OCF2CF(CF3)]nORfThe structure is shown in the specification, wherein n is an integer of 0-5, and RfIs a perfluoroalkyl group having 1 to 5 carbon atoms or a derivative containing a hydrogen atom.
Preferably, said has CF2＝CFCF2[OCF2CF(CF3)]nORfThe perfluoropropenyl alkoxy ether or the derivative containing hydrogen atom has the structure of CF2＝CFCF2OCF2CF(CF3)OCF3、CF2＝CFCF2OCF2CF(CF3)OC2F5、CF2＝CFCF2OCF2CF(CF3)OC3F7、CF2＝CFCF2OC3F7、CF2＝CFCF2OCF2CH2CF3Or CF2＝CFCF2OCF2CF(CF3)OCF2CH2CF3。
The preparation method of the tetrafluoroethylene-based copolymer comprises the following steps:
(1) adding a solvent and an emulsifier into an oxygen-free polymerization kettle, vacuumizing, adding an auxiliary agent, perfluoro-n-propyl vinyl ether, perfluoro-propenyl alkoxy ether or a hydrogen-containing derivative thereof and a chain transfer agent, and adding an initiator at 50-100 ℃ and 1.5-4.5 MPa for polymerization reaction;
(2) continuously adding tetrafluoroethylene into a polymerization kettle in the reaction process, and maintaining the temperature and the pressure in the polymerization kettle constant;
(3) and (3) after the tetrafluoroethylene is added in the step (2), cooling and emptying the polymerization kettle, coagulating, washing, drying and granulating the obtained emulsion to obtain the tetrafluoroethylene copolymer.
Wherein:
the solvent in the step (1) is deionized water, and the mass ratio of the amount of the deionized water to the tetrafluoroethylene in the step (2) is 3.67-4.33: 1.
The emulsifier in the step (1) is perfluoropolyether carboxylic acid or salt thereof, and the structural formula of the emulsifier is CF3CF2OCF2(OCF2)nX, wherein X is a carboxylic acid group or a salt thereof, n is an integer of 0 to 3, preferably CF3CF2OCF2OCF2COONH4Or CF3CF2OCF2OCF2COONa, the using amount of which is 1.07-1.6% of the total mass of the tetrafluoroethylene used in the step (2).
The auxiliary agent in the step (1) is perfluoroalkane or perfluorocycloalkane, and is selected from one, two or more of perfluorooctane, perfluoroheptane or perfluorocyclohexane, and the two or more are mixed at any ratio, and the dosage of the auxiliary agent is 1-10% of the mass of the solvent. The perfluoroalkane or perfluorocycloalkane is colorless and transparent and odorlessNon-toxic, non-inflammable and environment friendly. Perfluoroalkane or perfluorocycloalkane is added into polymerization system to raise PPVE and CF2＝CFCF2[OCF2CF(CF3)]nORfThe solubility in the solvent accelerates the polymerization reaction speed.
The usage amount of the perfluoro propenyl alkoxy ether or the hydrogen-containing derivative thereof in the step (1) is 1.33-4% of the total mass of the tetrafluoroethylene used in the step (2); the amount of the perfluoro-n-propyl vinyl ether is 3.33-10% of the total mass of the tetrafluoroethylene used in the step (2).
The chain transfer agent in the step (1) is methanol, ethanol, isopropanol, acetone, ethyl acetate, methane, n-hexane, cyclohexane, trichloromethane, dichloromethane or hydrogen, preferably methane, and the pressure of the added chain transfer agent in a polymerization kettle is increased by 0.4-0.8 MPa.
The initiator is a peroxide initiator, is selected from one, two or more of perfluoroacyl peroxide, potassium persulfate or ammonium persulfate, and is mixed at any ratio, preferably a mixture of the potassium persulfate and the ammonium persulfate, and the addition amount can be determined according to the required melt index.
The washing times in the step (3) are 4-6 times, the washing time is 2-4 hours, the drying temperature is 120-200 ℃, and the drying time is 4-6 hours.
Preferably, the reaction temperature in the step (1) is 50-90 ℃, and the pressure is 2.0-4.5 MPa.
More preferably, the reaction temperature in the step (1) is 80-90 ℃ and the pressure is 2.7-3.0 MPa.
Preferably, the method for preparing the tetrafluoroethylene-based copolymer according to the present invention comprises the steps of:
(1) adding a solvent and an emulsifier into an oxygen-free polymerization kettle, vacuumizing, adding an auxiliary agent, perfluoro-n-propyl vinyl ether and perfluoro-propenyl alkoxy ether or a hydrogen-containing derivative thereof, adding a chain transfer agent until the pressure in the polymerization kettle is increased by 0.4-0.8 MPa, and adding an initiator at 50-90 ℃ and 2.0-4.5 MPa for polymerization reaction;
(2) continuously adding tetrafluoroethylene into a polymerization kettle in the reaction process, and maintaining the temperature and the pressure in the polymerization kettle constant;
(3) and (3) after the addition of the tetrafluoroethylene in the step (2) is finished, cooling and emptying the polymerization kettle, coagulating the obtained emulsion, washing for 4-6 times by using deionized water, washing for 2-4 hours, drying for 4-6 hours at 120-200 ℃, and granulating by using a granulator to obtain the tetrafluoroethylene copolymer.
More preferably, the method for preparing a tetrafluoroethylene-based copolymer according to the present invention comprises the steps of:
(1) adding metered solvent and emulsifier into an oxygen-free polymerization kettle, vacuumizing, adding auxiliary agent, perfluoro-n-propyl vinyl ether and perfluoro-propenyl alkoxy ether or hydrogen-containing derivative thereof, adding chain transfer agent until the pressure in the polymerization kettle is increased by 0.4-0.8M Pa, and adding metered initiator according to the required melt index at 80-90 ℃ and 2.7-3.0 MPa for polymerization reaction;
(2) continuously adding tetrafluoroethylene into a polymerization kettle in the reaction process, and maintaining the temperature and the pressure in the polymerization kettle constant;
(3) and (3) after the addition of the tetrafluoroethylene in the step (2) is finished, cooling and emptying the polymerization kettle, coagulating the obtained emulsion, washing for 4-6 times by using deionized water, washing for 2-4 hours, drying for 4-6 hours at 120-200 ℃, and granulating by using a granulator to obtain the tetrafluoroethylene copolymer.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the polytetrafluoroethylene-based copolymer prepared by the invention, the perfluoro propenyl alkoxy ether or the hydrogen-containing derivative thereof is added, and the perfluoro propenyl alkoxy ether or the hydrogen-containing derivative thereof contains longer side chains, so that the polytetrafluoroethylene can be modified, the flexibility of the product is enhanced, the transparency is improved, the folding endurance life is longer than 200000 cycles, and the light transmittance is larger than 92%;
(2) the polytetrafluoroethylene-based copolymer prepared by the invention has good melt fluidity and thermal stability, the melt index is 2-32 g/10min, and the melting point is 300-310 ℃;
(3) the auxiliary agent perfluoroalkane or perfluorocycloalkane adopted by the preparation method is an environment-friendly solvent, and compared with the FC-113 solvent used in the traditional PFA polymerization system, the method avoids the damage to the atmospheric ozone layer caused by the use of the traditional FC-113 solvent, and is energy-saving and environment-friendly.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited thereto.
The starting materials used in the examples are all commercially available except where otherwise indicated.
Example 1
(1) To an oxygen free 100L stainless steel polymerization kettle, 60L deionized water, 500g ammonium perfluoropolyether carboxylate C F were added3CF2OCF2OCF2COONH4(40 wt.%) after the polymerization vessel was evacuated, 3kg of a mixture of perfluorooctane, perfluoroheptane and perfluorocyclohexane, 1000g of PPVE and 600g of perfluoropropenyl alkoxy ether CF were added2＝CFCF2OCF2C F(CF3)OC3F7Then filling methane to increase the pressure in the polymerization kettle by 0.5MPa, heating the polymerization kettle to 90 ℃, and quickly pumping the prepared 45g of mixed solution of potassium persulfate and ammonium persulfate into the polymerization kettle by an auxiliary agent pump when the pressure reaches 2.7MPa, wherein the mark of the start of the polymerization reaction is that the pressure in the polymerization kettle starts to decrease;
(2) continuously replenishing tetrafluoroethylene monomer in the polymerization process to maintain the temperature and pressure in the polymerization kettle constant;
(3) and stopping adding until the tetrafluoroethylene monomer consumes 15kg, emptying unreacted monomers, replacing the monomers with nitrogen, coagulating the emulsion, washing with 300L of water at 40 ℃ for 4 times, drying the polymer powder in an oven at 150 ℃ for 5 hours after washing for 3 hours to obtain polytetrafluoroethylene-based copolymer powder, and granulating by using a granulator to obtain the tetrafluoroethylene-based copolymer.
Example 2
(1) To an oxygen free 100L stainless steel polymerization kettle, 60L deionized water, 500g ammonium perfluoropolyether carboxylate C F were added3CF2OCF2OCF2COONH4(40 wt%) after evacuating the polymerization vessel, 5kg of a mixture of perfluorooctane, perfluoroheptane and perfluorocyclohexane, 80 wt% was added0g of PPVE and 300g of a perfluoropropenyl alkoxy ether CF2＝CFCF2OCF2CF(CF3)OC3F7Then filling methane to increase the pressure in the polymerization kettle by 0.6MPa, heating the polymerization kettle to 85 ℃, and quickly pumping the prepared 100g of mixed solution of potassium persulfate and ammonium persulfate into the polymerization kettle by an auxiliary agent pump when the pressure reaches 2.7MPa, wherein the mark of the start of the polymerization reaction is that the pressure in the polymerization kettle starts to decrease;
(2) continuously replenishing tetrafluoroethylene monomer in the polymerization process to maintain the temperature and pressure in the polymerization kettle constant;
(3) and stopping adding until the tetrafluoroethylene monomer consumes 15kg, emptying unreacted monomers, replacing the monomers with nitrogen, coagulating the emulsion, washing with 300L of water at 40 ℃ for 5 times, drying the polymer powder in an oven at 160 ℃ for 6 hours after washing for 3 hours to obtain polytetrafluoroethylene-based copolymer powder, and granulating by using a granulator to obtain the tetrafluoroethylene-based copolymer.
Example 3
(1) To an oxygen free 100L stainless steel polymerization kettle, 60L deionized water, 500g ammonium perfluoropolyether carboxylate C F were added3CF2OCF2OCF2COONH4(40 wt.%), after the polymerization vessel was evacuated, 5kg of a mixture of perfluorooctane, perfluoroheptane and perfluorocyclohexane, 600g of PPVE and 200g of perfluoropropenyl alkoxy ether CF were added2＝CFCF2OCF2CF(CF3)OC3F7Then filling methane to increase the pressure in the polymerization kettle by 0.6MPa, heating the polymerization kettle to 85 ℃, and quickly pumping 200g of prepared mixed solution of potassium persulfate and ammonium persulfate into the polymerization kettle by an auxiliary agent pump when the pressure reaches 2.7MPa, wherein the mark of the start of the polymerization reaction is that the pressure in the polymerization kettle starts to decrease;
(2) continuously replenishing tetrafluoroethylene monomer in the polymerization process to maintain the temperature and pressure in the polymerization kettle constant;
(3) and stopping adding until the tetrafluoroethylene monomer consumes 15kg, emptying unreacted monomers, replacing the monomers with nitrogen, coagulating the emulsion, washing the emulsion for 6 times by using 300L of water with the temperature of 40 ℃, drying the polymer powder in an oven with the temperature of 160 ℃ for 6 hours after washing for 4 hours to obtain polytetrafluoroethylene-based copolymer powder, and granulating by using a granulator to obtain the tetrafluoroethylene-based copolymer.
Example 4
(1) To an oxygen free 100L stainless steel polymerization kettle, 60L deionized water, 500g ammonium perfluoropolyether carboxylate C F were added3CF2OCF2OCF2COONH4(40 wt.%) after the inside of the polymerization vessel was evacuated, 5kg of a mixture of perfluorooctane, perfluoroheptane and perfluorocyclohexane, 800g of PPVE and 300g of perfluoropropenyl alkoxy ether CF were added2＝CFCF2OCF2CF(CF3)OCF2CH2CF3Then filling methane to increase the pressure in the polymerization kettle by 0.6MPa, heating the polymerization kettle to 85 ℃, and quickly pumping the prepared 100g of mixed solution of potassium persulfate and ammonium persulfate into the polymerization kettle by an auxiliary agent pump when the pressure reaches 2.7MPa, wherein the mark of the start of the polymerization reaction is that the pressure in the polymerization kettle starts to decrease;
(2) continuously replenishing tetrafluoroethylene monomer in the polymerization process to maintain the temperature and pressure in the polymerization kettle constant;
(3) and stopping adding until the tetrafluoroethylene monomer consumes 15kg, emptying unreacted monomers, replacing the monomers with nitrogen, coagulating the emulsion, washing the emulsion for 6 times by using 300L of water with the temperature of 40 ℃, drying the polymer powder in an oven with the temperature of 160 ℃ for 6 hours after washing for 4 hours to obtain tetrafluoroethylene copolymer powder, and granulating by using a granulator to obtain the tetrafluoroethylene copolymer.
Comparative example
(1) To an oxygen free 100L stainless steel polymerization kettle, 60L deionized water, 500g ammonium perfluoropolyether carboxylate C F were added3CF2OCF2OCF2COONH4(40 wt%), vacuumizing the polymerization kettle, adding 5kg of a mixture of perfluorooctane, perfluoroheptane and perfluorocyclohexane and 800g of PPVE, then filling methane to increase the pressure in the polymerization kettle by 0.6MPa, heating the polymerization kettle to 90 ℃, and quickly pumping the prepared 100g of mixed solution of potassium persulfate and ammonium persulfate into the polymerization kettle through an auxiliary agent pump when the pressure reaches 2.7MPa, wherein the mark of the start of the polymerization reaction is that the polymerization kettle is pumpedThe internal pressure begins to drop;
(2) continuously replenishing tetrafluoroethylene monomer in the polymerization process to maintain the temperature and pressure in the polymerization kettle constant;
(3) and stopping adding until the tetrafluoroethylene monomer consumes 15kg, emptying unreacted monomers, replacing the monomers with nitrogen, coagulating the emulsion, washing with 300L of water at 40 ℃ for 5 times, drying the polymer powder in an oven at 150 ℃ for 5 hours after washing for 3 hours to obtain polytetrafluoroethylene-based copolymer powder, and granulating by using a granulator to obtain the tetrafluoroethylene-based copolymer.
Performance testing
The tetrafluoroethylene-based copolymers prepared in examples 1 to 3 and comparative examples were subjected to unstable terminal group treatment, then melt index and melting point tests were performed, and the product pressed film was subjected to light transmittance and folding life tests, with the test results shown in table 1.
TABLE 1
Claims (9)
1. A tetrafluoroethylene-based copolymer characterized in that: the tetrafluoroethylene-based copolymer is a terpolymer containing 90-98 wt% of tetrafluoroethylene, 1-7 wt% of perfluoro-n-propyl vinyl ether and 1-3 wt% of perfluoro-propenyl alkoxy ether or a hydrogen-containing derivative thereof;
the perfluoropropenyl alkoxy ether or its hydrogen-containing derivative has CF2＝CFCF2[OCF2CF(CF3)]nORfThe structure is shown in the specification, wherein n is an integer of 0-5, and RfIs a perfluoroalkyl group having 1 to 5 carbon atoms or a derivative containing a hydrogen atom;
said has CF2＝CFCF2[OCF2CF(CF3)]nORfThe perfluoropropenyl alkoxy ether or the derivative containing hydrogen atom has the structure of CF2＝CFCF2OCF2CF(CF3)OCF3、CF2＝CFCF2OCF2CF(CF3)OC2F5、CF2＝CFCF2OCF2CF(CF3)OC3F7、CF2＝CFCF2OC3F7、CF2＝CFCF2OCF2CH2CF3Or CF2＝CFCF2OCF2CF(CF3)OCF2CH2C F3。
2. A method for producing a tetrafluoroethylene-based copolymer according to claim 1, characterized in that: the method comprises the following steps:
(1) adding a solvent and an emulsifier into an oxygen-free polymerization kettle, vacuumizing, adding an auxiliary agent, perfluoro-n-propyl vinyl ether, perfluoro-propenyl alkoxy ether or a hydrogen-containing derivative thereof and a chain transfer agent, and adding an initiator at 50-100 ℃ and 1.5-4.5 MPa for polymerization reaction;
(2) continuously adding tetrafluoroethylene into a polymerization kettle in the reaction process, and maintaining the temperature and the pressure in the polymerization kettle constant;
(3) and (3) after the tetrafluoroethylene is added in the step (2), cooling and emptying the polymerization kettle, coagulating, washing, drying and granulating the obtained emulsion to obtain the tetrafluoroethylene copolymer.
3. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the solvent in the step (1) is deionized water, and the mass ratio of the amount of the deionized water to the tetrafluoroethylene in the step (2) is 3.67-4.33: 1.
4. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the emulsifier in the step (1) is perfluoropolyether carboxylic acid or salt thereof, and the structural formula of the emulsifier is CF3CF2OCF2(OCF2)nX, wherein X is a carboxylic acid group or a salt thereof, n is an integer of 0 to 3, and the amount thereof is 1.07 to 1.6% by mass of the total amount of tetrafluoroethylene used in the step (2).
5. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the auxiliary agent in the step (1) is perfluoroalkane or perfluorocycloalkane, and is selected from one, two or more of perfluorooctane, perfluoroheptane or perfluorocyclohexane, and the dosage of the auxiliary agent is 1-10% of the mass of the solvent.
6. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the usage amount of the perfluoro propenyl alkoxy ether or the hydrogen-containing derivative thereof in the step (1) is 1.33-4% of the total mass of the tetrafluoroethylene used in the step (2); the using amount of the perfluoro-n-propyl vinyl ether is 3.33-10% of the total mass of the tetrafluoroethylene used in the step (2).
7. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the chain transfer agent in the step (1) is methanol, ethanol, isopropanol, acetone, ethyl acetate, methane, n-hexane, cyclohexane, trichloromethane, dichloromethane or hydrogen, and the pressure of the added chain transfer agent in a polymerization kettle is increased by 0.4-0.8 MPa.
8. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the initiator is a peroxide initiator and is selected from one, two or more of perfluoroacyl peroxide, potassium persulfate or ammonium persulfate.
9. The method for producing a tetrafluoroethylene-based copolymer according to claim 2, wherein: the washing times in the step (3) are 4-6 times, the washing time is 2-4 hours, the drying temperature is 120-200 ℃, and the drying time is 4-6 hours.
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