CN104945551A - Application of environment-friendly surfactant in synthesis of fluorine-containing polymer - Google Patents

Abstract

The invention discloses the application of an environment-friendly surfactant dialkyl phosphate ester salt and/or di-(2-ethylhexyl) phosphate in the synthesis of fluorine-containing polymers. The surfactant provided by the invention has good solubility and emulsification in water, low use concentration, biocompatibility and biodegradability, and the fluorine-containing resin matrix prepared by the surfactant has no residue in the body, is highly clean and has wide application.

Description

Application of an environmentally friendly surfactant in the synthesis of fluoropolymers

technical field

The invention belongs to the field of fluorine-containing polymer materials, and relates to the application of an environment-friendly surfactant in the synthesis of fluorine-containing polymers.

Background technique

Fluorine-containing polymer materials have excellent properties such as high and low temperature resistance, dielectric properties, chemical stability, weather resistance, non-combustibility, non-stickiness and low friction coefficient. An important material indispensable to industry. The main varieties of fluorine materials are polytetrafluoroethylene (PTFE), meltable polytetrafluoroethylene (PFA), polyvinyl fluoride (PVF), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), vinyl- Tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), vinylidene fluoride-hexafluoropropylene copolymer (FKM26), vinylidene fluoride -Tetrafluoroethylene-hexafluoropropylene copolymer (FKM246) and a series of modified fluorine-containing polymer materials, etc.

Ethylene-chlorotrifluoroethylene (ECTFE or F30) fluororesin, first synthesized by DuPont in the United States, is a thermoplastic fluorine-containing copolymer with extraordinary corrosion resistance to most inorganic and organic chemicals and organic solvents. Compared with other thermoplastics, ECTFE's resistance to chlorine and chlorine derivatives at high temperatures is particularly outstanding; it has good toughness, high hardness, and outstanding impact resistance. The surface of its finished material is extremely smooth, similar to glass. The proliferation of microorganisms is used in the fields of food and drinking water; ECTFE has excellent electrical properties, and the wires and cables made of ECTFE belong to the highest safety level. And other electrical equipment components, miniature potentiometer positive / negative thread sliders, battery boxes, electrical shrinkable tubes, etc., can be used safely in the temperature range from low temperature to 149 °C; the most important feature is that it is resistant to water vapor and Other gases have extremely low permeability, and are widely used in the internal and external spraying of dust-free and sterile air ducts in the electronics and pharmaceutical industries, anti-corrosion treatment of anti-corrosion equipment in chemical and other industries, solar energy packaging film materials and film applications in other fields.

Fluorosurfactant is the one with the highest surface activity among surfactants so far. It has been used in the manufacture of fluoropolymers for a long time. Its main function is to ensure the stability of the polymerization process of fluoropolymers and reduce the risk of water Surface tension, increasing the solubility of reaction monomers in water, constructing the state of primary particles and the cleanliness of reactors are necessary additives for the industrial production of fluorine-containing resins. In the past few decades, fluorine-containing surfactants represented by perfluorooctanoic acid compounds (abbreviated as PFOA) and perfluorosulfonyl compounds (abbreviated as PFOS) have played an important role in the production of fluoropolymers. . However, at the end of the last century, scientists discovered that PFOA or PFOS may have carcinogenic risks, so PFOA was included in the list of persistent organic pollutants (POPs). On November 11, 2004, the Stockholm Convention on Persistent Organic Pollutants, which aims to reduce and eliminate man-made emissions of persistent pollutants (POPs), officially entered into force for China. Fluorine chemical manufacturers all over the world are actively seeking and developing green alternatives to PFOA.

ECTFE resin can be prepared by solution polymerization, emulsion polymerization, microemulsion polymerization and suspension polymerization. Solution polymerization such as patents CA902848A, EP0612767B1, US4053445, US5182342, US5434229, etc. Microemulsion polymerization such as patent EP0712882B1. Suspension polymerization such as patents EP0747404B1, EP1067145B1. Emulsion polymerization such as patents US2559752, US4426501, US4789717, US5498680, US4482685, US3767634, US3857827, US4025709, US4225482, US6395848B1, US3006881, US3043823, US68699597, CA91, etc. These patents all adopt fluorine-containing (chlorine) type carboxylic acid or sulfonate surfactant or fluorine-containing alkyl ether type carboxylic acid and sulfonate type surfactant.

Therefore, it is necessary to develop new surfactants that can replace PFOA.

Contents of the invention

The purpose of the present invention is to provide an environment-friendly surfactant, which has good solubility and emulsification in water, low use concentration, biocompatibility and biodegradability, and can be used in the synthesis of fluorine-containing polymers.

For achieving the purpose of the invention, the technical scheme adopted by the present invention is:

An application of an environmentally friendly surfactant in the synthesis of fluoropolymers, characterized in that the environmentally friendly surfactant is selected from dialkyl phosphate ester salts and/or di-(2-ethylhexyl) phosphate;

The dialkyl phosphate salt has the following general structural formula (I):

Wherein: R is selected from C4-C12 straight chain alkyl, branched chain alkyl or cycloalkyl, M is selected from NH ₄ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ ;

The di-(2-ethylhexyl) phosphate has the following general structural formula (II):

Wherein: M is selected from NH ₄ ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ ;

The fluorine-containing polymer is selected from tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-trifluorochloroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-three Chlorofluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer or vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene copolymer.

As a preferred mode, in the above-mentioned dialkyl phosphate ester salt, R is preferably selected from n-butyl, hexyl or n-dodecyl, and M is selected from NH ⁴⁺ , Na ⁺ or K ⁺ ; the above-mentioned di-(2- In ethylhexyl) phosphate, M is preferably selected from NH ₄ ⁺ or Na ⁺ ; the mass percentage concentration of the above-mentioned environmentally friendly surfactant in the reaction medium is preferably 0.01-5%; the above-mentioned fluoropolymer is preferably selected from ethylene-tetrafluoro Ethylene copolymers, ethylene-chlorotrifluoroethylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers or vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene copolymers.

The above-mentioned ethylene-chlorotrifluoroethylene copolymer is preferably prepared by emulsion copolymerization or suspension copolymerization of ethylene and chlorotrifluoroethylene in the presence of an environment-friendly surfactant.

When adopting emulsion copolymerization to prepare, comprise the following steps:

(1) Add pure water and surfactant to the reactor, start the reactor to stir at a low speed, and vacuumize the reactor so that the oxygen content in the reactor is lower than 30ppm, and the mass percentage concentration of the surfactant in the reaction medium water is 2-5 %;

(2) Adding a chain transfer agent into the reactor, the amount of the chain transfer agent is 0.01-5% of the total mass of the reaction monomer ethylene and chlorotrifluoroethylene monomer;

(3) Add part of chlorotrifluoroethylene monomer and ethylene monomer into the reactor until the pressure inside the reactor is 0.2-5MPa;

(4) Raise the temperature to make the temperature in the reactor reach 10-120°C, increase the stirring speed of the reactor, add an initiator to the reactor to initiate the reaction, and continuously add the remaining chlorotrifluoroethylene monomer and ethylene monomer into the reactor , keep the pressure in the reactor within the range of ±0.01MPa of the set polymerization pressure;

(5) After the reaction, the emulsion material is coagulated, washed and dried to obtain ethylene-chlorotrifluoroethylene copolymer.

When adopting suspension copolymerization to prepare, comprise the following steps:

(1) Add pure water and surfactant to the reactor, start the reactor to stir at a low speed, and vacuumize the reactor so that the oxygen content in the reactor is lower than 30ppm, and the mass percentage concentration of the surfactant in the reaction medium water is 0.01-2 %;

(2) Adding a chain transfer agent into the reactor, the amount of the chain transfer agent is 0.01-5% of the total mass of the reaction monomer ethylene and chlorotrifluoroethylene monomer;

(3) Add part of chlorotrifluoroethylene monomer and ethylene monomer into the reactor until the pressure inside the reactor is 0.2-5MPa;

(4) Raise the temperature to make the temperature in the reactor reach 10-120°C, increase the stirring speed of the reactor, add an initiator to the reactor to initiate the reaction, and continuously add the remaining chlorotrifluoroethylene monomer and ethylene monomer into the reactor , keep the pressure in the reactor within the range of ±0.01MPa of the set polymerization pressure;

(5) After the reaction is finished, wash and dry the suspended particles to obtain the ethylene-chlorotrifluoroethylene copolymer.

In the preparation of the above-mentioned emulsion copolymerization or suspension copolymerization to prepare ethylene-chlorotrifluoroethylene copolymer, as a preferred mode, the polymerization temperature is preferably 10-120°C, more preferably 20-70°C; the polymerization pressure is preferably 0.2- 5MPa, more preferably 0.5～3Mpa; the chain transfer agent is preferably one, two or three of dichloromethane, chloroform and methylcyclopentane; the ethylene monomer and chlorotrifluoroethylene monomer They can be mixed uniformly and then added to the reactor, or can be added to the reactor independently; the oxygen content in the reactor is preferably lower than 10ppm. The initiator used in the present invention is preferably potassium persulfate and/or ammonium persulfate; when the oxidation-reduction composite system initiator, the initiator is preferably a combination of oxidizing agent and reducing agent, that is, the oxidizing agent is potassium persulfate and/or persulfate Ammonium sulfate and reducing agent are sodium bisulfite and/or sodium metasulfite.

The 1% weight decomposition temperature Td of the ethylene-chlorotrifluoroethylene copolymer TGA prepared above is 380-450° C., and the melt index is 0.1-50 g/10mim (275° C., 2.16 kg).

The above-mentioned ethylene-chlorotrifluoroethylene copolymer may further contain one, two or more combinations of the following monomers: CF ₂ =CF-CF ₃ , CHF=CH-CF ₃ , CH ₂ =CF-CF ₃ or _CH2 =CH- _CF3 .

Compared with the prior art, the environment-friendly surfactant provided by the invention has the following advantages: it completely replaces the fluorine-containing surfactant, is non-toxic and harmless to the environment and the human body, and is a green and environment-friendly surfactant; it is easy to wash and remove, There is no residue in the resin matrix, the resin is highly clean and has a wide range of uses.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to these specific implementations. Those skilled in the art will realize that the present invention covers all alternatives, modifications and equivalents as may be included within the scope of the claims.

Embodiment 1: suspension polymerization method, two-(2-ethylhexyl) ammonium phosphate is surfactant, inorganic peroxide initiator

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 5g of di-(2-ethylhexyl) phosphate to the reactor Ammonium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa. Add 10ml of chloroform and 2563g of chlorotrifluoroethylene into the reaction kettle through a metering device, stir and raise the temperature to 65°C. After the temperature of the system is constant, add ethylene into the reaction kettle with a compressor until the pressure is 3.5MPa, and use a metering pump to the reaction kettle. Add 200ml of aqueous solution containing 2.5g of potassium persulfate to the kettle to initiate the polymerization reaction, and continue to feed ethylene gas to maintain the pressure at 3.5MPa to keep the reaction going on. After 2.5 hours of reaction, add 50ml of potassium persulfate to the reaction kettle through a metering pump. Aqueous solution, after continuing to react for 2.5 hours, stop adding ethylene gas, lower the temperature, recover unreacted ethylene and chlorotrifluoroethylene monomer, put the material into the centrifuge through the discharge valve of the reactor, and use hot deionized water after dehydration The material was washed several times to obtain a white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2220 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.3%; the molar percentage of ethylene structural units was 49.7%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 6.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 423.5°C; the DSC data shows that the melting point of the copolymer is at 225°C.

Embodiment 2: suspension polymerization method, two-(dodecyl) phosphoric acid ester potassium salt is surfactant, inorganic peroxide initiator

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 4.5g di-(dodecyl)potassium phosphate to 6L high-purity deionized water in the reactor Salt, vacuum and nitrogen replacement for three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 20ml of methylcyclopentane and 2563g of chlorotrifluoroethylene into the reactor through a metering device, stir and heat up to 60°C. After the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 2.8MPa. Add 200ml aqueous solution containing 2.35g ammonium persulfate into the reaction kettle by the metering pump to initiate the polymerization reaction, continue to feed ethylene gas to maintain the pressure at 2.8MPa to keep the reaction going on, after 3 hours of reaction, add 50ml to the reaction kettle through the metering pump Contain ammonium persulfate aqueous solution, continue to react for 3 hours, stop adding ethylene gas, cool down, recover unreacted ethylene and chlorotrifluoroethylene monomers, put the materials into the centrifuge through the discharge valve of the reactor, and use heat to dehydrate Wash the material several times with deionized water to obtain a white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2310 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 51.2%; the molar percentage of ethylene structural units was 48.8%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 10.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 418.2°C; the DSC data shows that the melting point of the copolymer is at 227°C.

Embodiment 3: suspension polymerization method, dibutyl phosphate sodium salt is surfactant, oxidation-reduction initiator

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.5L high-purity deionized water, 7.2g dibutyl phosphate sodium salt into the reactor, vacuumize and fill Nitrogen was replaced three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 5ml of chloroform, 4ml of methylcyclopentane, and 2500g of chlorotrifluoroethylene into the reactor through a metering device, add 700ml of an aqueous solution containing 7.5g of potassium persulfate into the reactor with a metering pump, stir and heat up to 35°C, and wait for the system to After the temperature is constant, add ethylene into the reactor with a compressor until the pressure is 1.65 MPa, and add 100 ml of an aqueous solution containing 1.5 g of sodium sulfite into the reactor with a metering pump to initiate the reaction and start polymerization. Continue to feed ethylene gas to maintain the pressure at 1.65MPa to keep the reaction going. After 3 hours of reaction, add 100ml of aqueous solution containing 1.5g of sodium sulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop adding ethylene gas, cool down and recover Unreacted ethylene and chlorotrifluoroethylene monomers are put into the centrifuge through the discharge valve of the reactor, and after dehydration, the materials are washed with hot deionized water for many times to obtain white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2320 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.05%; the molar percentage of ethylene structural units was 49.95%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 8.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 412.35°C; the DSC data shows that the melting point of the copolymer is at 238.5°C. Embodiment 4: Suspension polymerization method, di-(2-ethylhexyl) phosphoric acid ester sodium salt is surfactant, oxidation-reduction complex initiator

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 6.2g di-(2-ethylhexyl) phosphate to the reactor Sodium, evacuated and replaced with nitrogen three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 4ml chloroform, 7ml methylcyclopentane, 2500g chlorotrifluoroethylene to the reaction kettle through a metering device, add 200ml aqueous solution containing 1.5g potassium persulfate and 1.2g ammonium persulfate to the reaction kettle with a metering pump, stir and Raise the temperature to 35°C, and when the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 1.5MPa, and add 100ml of aqueous solution containing 0.4g of sodium sulfite and 0.75g of sodium metasulfite into the reactor with a metering pump to initiate the reaction and start polymerization . Continue to feed ethylene gas to maintain the pressure at 1.5MPa to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.25g of sodium sulfite and 0.45g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop the ethylene gas Add, cool down, recover unreacted ethylene and chlorotrifluoroethylene monomers, put the materials into the centrifuge through the discharge valve of the reactor, wash the materials with hot deionized water several times after dehydration, and obtain white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2410 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in the fluororesin was 51.03%; the molar percentage of ethylene structural units was 48.97%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 4.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 410.75°C; the DSC data shows that the melting point of the copolymer is at 240.1°C.

Embodiment 5: Emulsion polymerization, di-(2-ethylhexyl) phosphate sodium salt is surfactant, oxidation-reduction reaction

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 20.2g di-(2-ethylhexyl) phosphate to the reactor Sodium, evacuated and replaced with nitrogen three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 10ml of methylcyclopentane and 2500g of chlorotrifluoroethylene into the reactor through a metering device, add 200ml of an aqueous solution containing 1.5g of potassium persulfate and 1.2g of ammonium persulfate into the reactor with a metering pump, stir and heat up to 35 ℃, after the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 1.6MPa, add 100ml of aqueous solution containing 0.45g of sodium sulfite and 0.76g of sodium metasulfite into the reactor with a metering pump to initiate the reaction and start polymerization. Continue to feed ethylene gas to maintain the pressure at 1.6MPa to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.27g of sodium sulfite and 0.48g of sodium metasulfite to the reactor through a metering pump. After continuing the reaction for 3 hours, stop the ethylene gas Add, cool down, recover unreacted ethylene and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration to obtain white Powder ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2248 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.82%; the molar percentage of ethylene structural units was 49.18%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 11.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 409.5°C; the DSC data shows that the melting point of the copolymer is at 238.91°C.

Embodiment 6: Emulsion polymerization, di-(2-ethylhexyl) phosphate potassium salt is surfactant, oxidation-reduction reaction

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water and 18g di-(2-ethylhexyl) phosphate to the reactor Potassium, evacuated and replaced with nitrogen three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 12ml of methylcyclopentane and 2500g of chlorotrifluoroethylene to the reactor through a metering device, add 500ml of an aqueous solution containing 2.7g of potassium persulfate and 2.2g of ammonium persulfate into the reactor with a metering pump, stir and heat up to 45 ℃, after the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 2.6MPa, and add 100ml of an aqueous solution containing 1.92g of sodium metasulfite into the reactor with a metering pump to initiate the reaction and start polymerization. Continue feeding ethylene gas to keep the pressure at 2.6MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.5g sodium metasulfite to the reactor through a metering pump. After continuing the reaction for 3 hours, stop the addition of ethylene gas, cool down, Recover unreacted ethylene and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration to obtain white powder ECTFE fluororesin . The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2348 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.67%; the molar percentage of ethylene structural units was 49.33%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 21.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 400.5°C; the DSC data shows that the melting point of the copolymer is at 219.95°C.

Embodiment 7: Emulsion polymerization, two-(dodecyl) phosphate ammonium salt is surfactant, oxidation reaction

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water, 42g di-(dodecyl) ammonium phosphate to the reactor , Vacuumize and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to vacuumize until the pressure inside the reactor is -0.1MPa. Add 9ml of methylcyclopentane and 2500g of chlorotrifluoroethylene to the reactor through a metering device, add 500ml of an aqueous solution containing 2.7g of potassium persulfate and 2.2g of ammonium persulfate into the reactor with a metering pump, stir and heat up to 65 ℃, after the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 2.6MPa, and add 100ml of aqueous solution containing 1.04g of sodium bisulfite into the reactor with a metering pump to initiate the reaction and start polymerization. Continue feeding ethylene gas to keep the pressure at 2.6MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.1g sodium bisulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop adding ethylene gas. Cool down and recover unreacted ethylene and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation barrel through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration to obtain white powder ECTFE Fluorine resin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2348 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.63%; the molar percentage of ethylene structural units was 49.37%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 20.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 399.5°C; the DSC data shows that the melting point of the copolymer is at 218.95°C.

Embodiment 8: Suspension polymerization method, di-(dodecyl) phosphate potassium salt is surfactant, inorganic peroxide initiator (ternary copolymerization)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 4.5g di-(dodecyl)potassium phosphate to 6L high-purity deionized water in the reactor Salt, vacuum and nitrogen replacement for three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 12ml of methylcyclopentane, 2563g of chlorotrifluoroethylene, and 250g of hexafluoropropylene into the reaction kettle through a metering device, stir and raise the temperature to 60°C. After the temperature of the system is constant, add ethylene into the reaction kettle with a compressor to pressure to 2.92MPa, add 200ml aqueous solution containing 2.35g ammonium persulfate to the reactor with a metering pump to initiate the polymerization reaction, continue to feed ethylene gas to maintain the pressure at 2.92MPa to keep the reaction going, after 3 hours of reaction, the metering pump is used to feed the reaction Add 50ml of ammonium persulfate-containing aqueous solution to the kettle, continue to react for 3 hours, stop adding ethylene gas, cool down, recover unreacted ethylene, chlorotrifluoroethylene, and hexafluoropropylene monomers, and discharge the materials through the reactor discharge valve. Put it into a centrifuge, wash the material with hot deionized water several times after dehydration, and obtain a white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2400 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.2%; the molar percentage of hexafluoropropylene structural units was 1.7%; the molar percentage of ethylene structural units was Min content is 48.1%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 12.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 400.2°C; the DSC data shows that the melting point of the copolymer is at 212.8°C.

Example 9: Suspension polymerization method, dibutyl phosphate sodium salt as surfactant, oxidation-reduction initiator (ternary copolymerization)

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.5L high-purity deionized water, 5.8g dibutyl phosphate sodium salt into the reactor, vacuumize and fill Nitrogen was replaced three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 4ml of chloroform, 6ml of methylcyclopentane, 2500g of chlorotrifluoroethylene, 150g of 3,3,3-trifluoromethylpropene into the reactor through a metering device, and add 700ml of 7.5g of persulfuric acid into the reactor with a metering pump Potassium aqueous solution, stir and heat up to 35°C. After the temperature of the system is constant, add ethylene into the reactor with a compressor until the pressure is 1.7MPa, and add 100ml of aqueous solution containing 1.5g of sodium sulfite into the reactor with a metering pump to initiate the reaction and start polymerization . Continue to feed ethylene gas to maintain the pressure at 1.7MPa to keep the reaction going. After 3 hours of reaction, add 100ml of aqueous solution containing 1.5g of sodium sulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop adding ethylene gas, cool down and recover Unreacted ethylene, 3,3,3-trifluoromethylpropene, and chlorotrifluoroethylene monomers are put into the centrifuge through the discharge valve of the reactor, and the materials are washed with hot deionized water several times after dehydration , to obtain a white fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2360 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in the fluororesin was 49.5%; the molar percentage of 3,3,3-trifluoromethylpropene structural units was 1.1% ; Ethylene structure unit mole percentage is 49.4%.

Polymer data: The melt index of the fluororesin measured by the melt index meter is 10.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 414.5°C; the DSC data shows that the melting point of the copolymer is at 225.5°C.

Embodiment 10: Emulsion polymerization, di-(dodecyl) phosphate ammonium salt is surfactant, oxidation reaction (ternary copolymerization)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water, 45g di-(dodecyl) ammonium phosphate to the reactor ,, Vacuumize and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to vacuumize until the pressure inside the reactor is -0.1MPa. Add 8.2ml methylcyclopentane, 2500g chlorotrifluoroethylene, 180g 2,3,3,3-tetrafluoropropene into the reactor through a metering device, add 500ml containing 2.7g potassium persulfate and 2.2g ammonium persulfate aqueous solution, stir and heat up to 65°C. After the system temperature is constant, add ethylene into the reaction kettle with a compressor until the pressure is 2.6MPa, and add 100ml containing 1.04g sulfurous acid into the reaction kettle with a metering pump. Sodium hydrogen aqueous solution, initiate the reaction and start polymerization. Continue feeding ethylene gas to keep the pressure at 2.6MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.1g sodium bisulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop adding ethylene gas. Cool down and recover unreacted ethylene, 2,3,3,3-tetrafluoropropene, and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation barrel through the discharge valve of the reactor, and use hot water after coagulation and dehydration Wash the material several times with deionized water to obtain white powder fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2400 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in the fluororesin was 50.63%; the molar percentage of 2,3,3,3-tetrafluoropropene structural units was 1.0% ; Ethylene structure unit mole percentage is 48.37%.

Polymer data: The melt index of the fluororesin measured by the melt index meter is 25.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 395.5°C; the DSC data shows that the melting point of the copolymer is at 216°C.

Embodiment 11: Suspension polymerization method, di-(dodecyl) phosphate potassium salt is surfactant, inorganic peroxide initiator (ternary copolymerization, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene elastic body)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.5g di-(dodecyl)potassium phosphate to 6L high-purity deionized water in the reactor Salt, vacuum and nitrogen replacement for three times, the oxygen content was determined to be below 10ppm, and the vacuum was continued until the pressure in the reactor was -0.1MPa. Add 6ml of methylcyclopentane, 2563g of chlorotrifluoroethylene, and 1000g of hexafluoropropylene into the reaction kettle through a metering device, stir and raise the temperature to 55°C. After the temperature of the system is constant, add vinylidene fluoride into the reaction kettle with a compressor When the pressure is 3.02MPa, add 200ml aqueous solution containing 2.35g ammonium persulfate to the reactor to initiate the polymerization reaction with a metering pump, and continue to feed vinylidene fluoride gas to maintain the pressure at 3.02MPa to keep the reaction going. After 3 hours of reaction, pass The metering pump adds 50ml of ammonium persulfate-containing aqueous solution to the reaction kettle, and after continuing to react for 3 hours, stop the addition of ethylene gas, cool down, recover unreacted vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene monomers, and pass through the reaction kettle The discharge valve puts the material into the centrifuge, and washes the material with hot deionized water several times after dehydration to obtain white fluororesin powder. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2900 g of fluororesin.

The elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene in the fluororesin was 49.0%; the molar percentage of hexafluoropropylene was 6.7%; the molar percentage of vinylidene fluoride The mole percentage is 44.3%.

Example 12: Emulsion polymerization, di-(2-ethylhexyl) phosphate potassium salt as surfactant, oxidation-reduction reaction (vinylidene fluoride-chlorotrifluoroethylene copolymer)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water and 18g di-(2-ethylhexyl) phosphate to the reactor Potassium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa. Add 5ml of methylcyclopentane and 2500g of chlorotrifluoroethylene into the reactor through a metering device, add 500ml of an aqueous solution containing 2.7g of potassium persulfate and 2.2g of ammonium persulfate into the reactor with a metering pump, stir and heat up to 45 ℃, after the temperature of the system is constant, add vinylidene fluoride into the reaction kettle with a compressor until the pressure is 2.56MPa, and add 100ml of an aqueous solution containing 1.92g of sodium metasulfite into the reaction kettle with a metering pump to initiate the reaction and start polymerization. Continue to feed vinylidene fluoride gas to maintain the pressure at 2.56MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.5g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop the vinylidene fluoride gas Add, cool down, recover unreacted vinylidene fluoride and chlorotrifluoroethylene monomer, put the white emulsion material into the coagulation barrel through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration. A white powder ECTFE resin was obtained. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2108 g of resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 65.67%; the molar percentage of vinylidene fluoride structural units was 34.33%.

Example 13: Emulsion polymerization, di-(2-ethylhexyl) phosphate potassium salt as surfactant, oxidation-reduction reaction (vinylidene fluoride-hexafluoropropylene copolymer)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water and 22g di-(2-ethylhexyl) phosphate to the reactor Potassium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa. Add 2.5ml of methylcyclopentane and 1500g of hexafluoropropylene into the reactor through a metering device, add 500ml of an aqueous solution containing 2.7g of potassium persulfate and 2.2g of ammonium persulfate into the reactor with a metering pump, stir and heat up to 40 ℃, after the temperature of the system is constant, add vinylidene fluoride into the reaction kettle with a compressor until the pressure is 2.5MPa, and add 100ml of aqueous solution containing 1.92g of sodium metasulfite into the reaction kettle with a metering pump to initiate the reaction and start polymerization. Continue to feed vinylidene fluoride gas to maintain the pressure at 2.5MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.5g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 3 hours, stop the vinylidene fluoride gas Add, cool down, recover unreacted vinylidene fluoride and hexafluoropropylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, wash the material with hot deionized water several times after coagulation and dehydration, and obtain White ECTFE resin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1508 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of hexafluoropropylene structural units in ECTFE resin was 10.67%; the molar percentage of vinylidene fluoride structural units was 89.33%.

The following example 14-polymerization is carried out in the form of mixed gas feeding. Two gas mixers need to be equipped in the reaction device. For different fluoropolymers: the molar ratio of the monomers in the No. 1 gas mixer is based on the competitive polymerization of different monomers The rate is determined; the ratio of monomers in the No. 2 gas mixer is determined according to the polymer structure.

Embodiment 14: Suspension polymerization method, mixed gas feed, two-(2-ethylhexyl) phosphoric acid ester ammonium salt is surfactant, inorganic peroxide initiator

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 5.5g di-(2-ethylhexyl) phosphate to the reactor Ammonium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa. Stir and heat up to 65°C. After the temperature of the system is constant, pass the gas in the No. 1 gas mixer into the reaction kettle through the compressor until the pressure is 3.5MPa. Add 9.5ml chloroform and 200ml containing 2.5g aqueous solution of potassium persulfate to initiate the polymerization reaction, the gas in the No. 2 gas mixer is passed into the reactor through the compressor, and the reaction pressure is kept at 3.5MPa to continue the reaction. Add 50ml of potassium persulfate-containing aqueous solution, continue the reaction for 2.5 hours, stop adding the mixed gas, lower the temperature, recover unreacted ethylene and chlorotrifluoroethylene monomers, put the materials into the centrifuge through the discharge valve of the reactor, After dehydration, wash the material with hot deionized water several times to obtain a white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1950 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 51.3%; the molar percentage of ethylene structural units was 48.7%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 5.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 410.5°C; the DSC data shows that the melting point of the copolymer is at 227.2°C.

Embodiment 15: Suspension polymerization method, mixed gas feed, di-(dodecyl) phosphate potassium salt is surfactant, inorganic peroxide initiator

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water, 6.5g di-(dodecyl) potassium phosphate to the reactor Salt, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 60°C, after the temperature of the system is constant, add it into the reactor with a compressor The pressure of the gas in the No. 1 mixer to the reactor is 2.8MPa. Add 22ml methylcyclopentane and 200ml aqueous solution containing 2.35g ammonium persulfate to the reactor with a metering pump to initiate the polymerization reaction, and continue to pass into the reactor No. 2. The gas keeps the pressure of the reactor at 2.8MPa to keep the reaction going. After 3 hours of reaction, add 50ml of ammonium persulfate aqueous solution to the reactor through a metering pump. After continuing the reaction for 3 hours, stop adding the mixed gas, cool down, and recover unreacted The ethylene and chlorotrifluoroethylene monomers are put into the centrifuge through the discharge valve of the reactor. After dehydration, the materials are washed with hot deionized water for many times to obtain white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2002 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.2%; the molar percentage of ethylene structural units was 49.8%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 20.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 415.2°C; the DSC data shows that the melting point of the copolymer is at 225.8°C.

Example 16: Suspension polymerization method, mixed gas feed, dibutyl phosphate sodium salt as surfactant, oxidation-reduction composite initiator

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.5L high-purity deionized water and 8.2g dibutyl phosphate sodium salt into the reactor, vacuumize and fill Nitrogen was replaced three times, and the oxygen content was determined to be below 10ppm. Continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 35°C. Gas until the pressure of the reactor is 1.65MPa, add 5ml chloroform, 6ml methylcyclopentane, and 700ml aqueous solution containing 7.5g potassium persulfate to the reactor with a metering pump, and then use a metering pump to inject Add 100ml of aqueous solution containing 1.5g of sodium sulfite to initiate the reaction and start polymerization. Use a compressor to continuously feed the gas in No. 2 reactor to the reactor to maintain the pressure of the reactor at 1.65MPa to make the reaction continue. After reacting for 3 hours, add 100ml of aqueous solution containing 1.5g of sodium sulfite to the reactor through a metering pump, and continue After reacting for 3 hours, stop adding the mixed gas, lower the temperature, recover unreacted ethylene and chlorotrifluoroethylene monomer, put the material into the centrifuge through the discharge valve of the reactor, and wash it with hot deionized water several times after dehydration Material, obtains white ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1920 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.25%; the molar percentage of ethylene structural units was 49.75%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 12.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 408.55°C; the DSC data shows that the melting point of the copolymer is at 240°C.

Example 17: Suspension polymerization method, mixed gas feed, di-(2-ethylhexyl) phosphate sodium salt as surfactant, oxidation-reduction composite initiator

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating, and circulating cooling water, and add 6L high-purity deionized water and 7.52g of di-(2-ethylhexyl) phosphate to the reactor Sodium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue vacuuming until the pressure in the reactor is -0.1MPa, add 200ml containing 1.5g potassium persulfate and 1.2g ammonium persulfate to the reactor with a metering pump Stir and heat up to 35°C. After the temperature of the system is constant, add the gas in the No. 1 mixer to the reactor with a compressor until the pressure of the reactor is 1.5MPa, and add 6ml chloroform, 6ml Methylcyclopentane, 100ml containing 0.4g sodium sulfite and 0.75g sodium metasulfite aqueous solution, initiates the reaction to start polymerization. Use a compressor to continuously feed the gas in No. 2 reactor into the reactor to maintain the pressure of the reactor at 1.5MPa to continue the reaction. After 3 hours of reaction, add 50ml of 0.25g sodium sulfite and 0.45g sodium sulfite to the reactor through a metering pump. Sodium metasulfite aqueous solution, continue to react for 3 hours, stop adding the mixed gas, cool down, recover unreacted ethylene and chlorotrifluoroethylene monomer, put the material into the centrifuge through the discharge valve of the reaction kettle, dehydrate and use hot water to remove Ionized water washed the material several times to obtain white ECTFE resin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1860 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.0%; the molar percentage of ethylene structural units was 50.0%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 9.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 410.8°C; the DSC data shows that the melting point of the copolymer is at 240.1°C.

Example 18: Emulsion polymerization, mixed gas feed, di-(2-ethylhexyl) phosphate ammonium salt as surfactant, oxidation-reduction reaction

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 40.0g di-(2-ethylhexyl) phosphate to the reactor Ammonium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 35°C, and pass the gas in the No. 1 gas mixer into the reaction through the compressor Still, until the pressure is 1.72MPa, then add 200ml of aqueous solution containing 1.5g potassium persulfate and 1.2g ammonium persulfate to the reaction kettle with a metering pump. After the temperature of the system is constant, add 9ml formazan Cyclopentane, 100ml contains 0.45g sodium sulfite and 0.76g sodium metasulfite aqueous solution to initiate the reaction, add the mixed gas in No. 2 mixed gas to the reactor with a compressor, and maintain the reaction pressure at 1.72MPa. Continue to feed No. 2 mixed gas to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.27g of sodium sulfite and 0.48g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 5 hours, stop adding the mixed gas and cool down. 1. Recover unreacted ethylene and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration to obtain white powder ECTFE resin . The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1560 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.05%; the molar percentage of ethylene structural units was 49.95%.

Polymer data: The melt index of the resin measured by the melt index meter is 13.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 400.5°C; the DSC data shows that the melting point of the copolymer is 239.9 ℃.

Example 19: Emulsion polymerization, mixed gas feed, di-(2-ethylhexyl) phosphate potassium salt as surfactant, oxidation-reduction reaction

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water and 28g di-(2-ethylhexyl) phosphate to the reactor Potassium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 45°C, after the temperature of the system is constant, add it into the reactor with a metering pump 500ml of aqueous solution containing 2.7g potassium persulfate and 2.2g ammonium persulfate, add the gas in the No. 1 mixer to the reactor with a compressor until the pressure of the reactor is 2.6MPa, add 15ml of methylcyclosulfate into the reactor with a metering pump Pentane, 100ml containing 1.92g sodium metasulfite aqueous solution, initiates the reaction and begins to polymerize. Continue to feed the mixed gas in the No. 2 mixer to maintain the pressure at 2.6MPa to keep the reaction going. After 2.5 hours of reaction, add 100ml of aqueous solution containing 1.5g of sodium metasulfite to the reaction kettle through the metering pump, continue the reaction for 3 hours, and then stop Mixed gas is added, the temperature is lowered, and unreacted ethylene and chlorotrifluoroethylene monomers are recovered. The white emulsion material is put into the coagulation bucket through the discharge valve of the reactor. After coagulation and dehydration, the material is washed with hot deionized water for many times. A white powder ECTFE resin was obtained. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2348 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.5%; the molar percentage of ethylene structural units was 49.5%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 18.25g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 401.5°C; the DSC data shows that the melting point of the copolymer is at 217.2°C.

Example 20: Emulsion polymerization, mixed gas feed, di-(dodecyl) phosphate ammonium salt as surfactant, oxidation-reduction reaction

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 5.7L high-purity deionized water, 42g di-(dodecyl) ammonium phosphate to the reactor , evacuate and replace with nitrogen for three times, measure the oxygen content below 10ppm, continue vacuuming until the pressure in the reactor is -0.1MPa, stir and heat up to 40°C, add the mixed gas in the No. 1 mixer to the reactor with a compressor When the pressure is 2.6MPa, add 500ml of aqueous solution containing 2.7g of potassium persulfate and 2.2g of ammonium persulfate into the reactor with a metering pump, and after the temperature of the system is constant, add 9ml of methylcyclopentane into the reactor with a metering pump , 100ml containing 1.04g sodium bisulfite aqueous solution, trigger the reaction to start polymerization. Add mixed gas in No. 2 mixer with compressor to keep reaction pressure in reactor and keep reaction pressure as 2.6MPa to make reaction continue. After reacting for 2.5 hours, add 100ml containing 1.1g sodium bisulfite aqueous solution in reactor by metering pump, After continuing to react for 3 hours, stop adding the mixed gas, lower the temperature, recover unreacted ethylene and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation barrel through the discharge valve of the reactor, and use hot water to remove it after coagulation and dehydration. Wash the material several times with ionized water to obtain white powder ECTFE fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1500 g of ECTFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in ECTFE resin was 50.23%; the molar percentage of ethylene structural units was 49.77%.

Polymer data: The melt index of ECTFE resin measured by the melt index meter is 15.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 401.5°C; the DSC data shows that the melting point of the copolymer is at 216.95°C.

Example 21: Suspension polymerization method, mixed gas feed, di-(2-ethylhexyl) phosphate ammonium salt as surfactant, inorganic peroxide initiator (ternary copolymerization)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 5.5g di-(2-ethylhexyl) phosphate to the reactor Ammonium, evacuate and replace with nitrogen three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa. Stir and heat up to 65°C, add 300g of hexafluoropropylene into the reaction kettle with a liquid-phase metering pump, and after the system temperature is constant, pass the gas in the No. 1 gas mixer into the reaction kettle through a compressor until the pressure is 3.5MPa Add 6.5ml chloroform, 200ml containing 2.5g potassium persulfate aqueous solution to initiate polymerization reaction in reactor with other metering pumps again, pass in the reactor in No. 2 gas mixer by compressor, keep reaction pressure at 3.5 MPa makes the reaction continue, after reacting for 2.5 hours, add 50ml of potassium persulfate aqueous solution by metering pump in the reactor, after continuing to react for 2.5 hours, stop the mixed gas to add, lower the temperature, reclaim unreacted ethylene, hexafluoropropylene, Chlorotrifluoroethylene monomer, put the material into the centrifuge through the discharge valve of the reactor, wash the material with hot deionized water several times after dehydration, and obtain the white fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2000 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of trifluoroethylene structural units in the fluororesin was 50.63%; the molar percentage of hexafluoropropylene structural units was 1.57%; the molar percentage of ethylene structural units was Min content is 47.8%.

Polymer data: The melt index of the fluororesin measured by the melt index meter is 10.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 405.5°C; the DSC data shows that the melting point of the copolymer is at 220.2°C.

Example 22: Emulsion polymerization, mixed gas feed, di-(2-ethylhexyl) phosphate ammonium salt as surfactant, oxidation-reduction reaction (ternary copolymerization)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 40.0g di-(2-ethylhexyl) phosphate to the reactor Ammonium, replaced by vacuuming and filling nitrogen three times, measuring the oxygen content below 10ppm, continuing to vacuumize until the pressure in the reactor is -0.1MPa, stirring and raising the temperature to 35°C, adding 1,3, 220g of 3,3-tetrafluoropropene; pass the gas in the No. 1 gas mixer into the reactor through the compressor until the pressure is 1.72MPa, and then add 200ml containing 1.5g potassium persulfate and 1.2 g ammonium persulfate aqueous solution, after the temperature of the system is constant, add 9ml methylcyclopentane to the reaction kettle with a metering pump, 100ml containing 0.45g sodium sulfite and 0.76g sodium metasulfite aqueous solution to initiate the reaction, and use the compressor to the reaction kettle Add the mixed gas in No. 2 mixed gas to maintain the reaction pressure at 1.72MPa. Continue to feed No. 2 mixed gas to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.27g of sodium sulfite and 0.48g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 5 hours, stop adding the mixed gas and cool down. , Recover unreacted ethylene, 1,3,3,3-tetrafluoropropene, and chlorotrifluoroethylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, and use hot water to remove the condensate after coagulation and dehydration Wash the material several times with ionized water to obtain white powder fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1580 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of chlorotrifluoroethylene structural units in the fluororesin was 50.05%; the molar percentage of 1,3,3,3-tetrafluoropropene structural units was 0.5% ; Ethylene structure unit mole percentage is 49.45%.

Polymer data: The melt index of the fluororesin measured by the melt index meter is 29.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 385.5°C; the DSC data shows that the melting point of the copolymer is at 226°C.

Example 23: Suspension polymerization method, mixed gas feed, di-(dodecyl) phosphate potassium salt as surfactant, inorganic peroxide initiator (ethylene-tetrafluoroethylene polymer)

Clean the 10L stainless steel high-pressure reactor equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water, 6.5g di-(dodecyl) potassium phosphate to the reactor Salt, evacuate and replace with nitrogen for three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 45°C, after the temperature of the system is constant, add it into the reactor with a compressor The gas in the No. 1 mixer (ethylene:tetrafluoroethylene=60:40) to the pressure of the reactor is 3.2MPa, and the metering pump is used to add 5ml methylcyclopentane and 200ml aqueous solution containing 2.35g ammonium persulfate to the reactor to trigger For the polymerization reaction, continue to feed the gas in the No. 2 reactor (ethylene:tetrafluoroethylene=50:50) to maintain the pressure of the reactor at 3.2MPa to continue the reaction. After 3 hours of reaction, add 50ml to the reactor through the metering pump Contain ammonium persulfate aqueous solution, continue to react for 3 hours, stop adding mixed gas, cool down, recover unreacted ethylene and tetrafluoroethylene monomers, put the materials into the centrifuge through the discharge valve of the reactor, and use hot The material was washed several times with deionized water to obtain a white ETFE resin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1602 g of ETFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of tetrafluoroethylene structural units in ETFE resin was 50.2%; the molar percentage of ethylene structural units was 49.8%.

Polymer data: The melt index of ETFE resin measured by the melt index meter is 2.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 435.2°C; the DSC data shows that the melting point of the copolymer is at 258.8°C.

Example 24: Suspension polymerization method, mixed gas feed, di-(dodecyl) phosphate potassium salt as surfactant, inorganic peroxide initiator (vinylidene fluoride-hexafluoropropylene polymer)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water, 7.5g di-(dodecyl)potassium phosphate to the reactor Salt, evacuate and replace with nitrogen for three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 50°C, after the temperature of the system is constant, add it into the reactor with a compressor The gas in the No. 1 mixer (vinylidene fluoride: hexafluoropropylene=55:45) to the pressure of the reactor is 2.5MPa, and the metering pump is used to add 12.5ml methylcyclopentane and 200ml containing 2.35g ammonium persulfate to the reactor The aqueous solution is used to initiate the polymerization reaction, and the gas in the No. 2 reactor (vinylidene fluoride: hexafluoropropylene = 78: 22) is continuously introduced to maintain the pressure of the reactor at 2.5MPa to keep the reaction going. Add 50ml of aqueous solution containing ammonium persulfate to the kettle, and after continuing to react for 3 hours, stop adding the mixed gas, cool down, recover unreacted vinylidene fluoride and hexafluoropropylene monomer, and put the materials into the centrifuge through the discharge valve of the reaction kettle After dehydration, the material was washed with hot deionized water several times to obtain a white fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1700 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of vinylidene fluoride structural units in the fluororesin was 85.2%; the molar percentage of ethylene structural units was 14.8%.

Embodiment 25: Suspension polymerization method, mixed gas feed, di-(dodecyl) phosphate potassium salt is surfactant, inorganic peroxide initiator (vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene polymer )

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water, 7.5g di-(dodecyl)potassium phosphate to the reactor Salt, evacuate and replace with nitrogen for three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 50°C, after the temperature of the system is constant, add it into the reactor with a compressor The gas in No. 1 mixer (vinylidene fluoride: tetrafluoroethylene: hexafluoropropylene = 44:14:42) until the pressure of the reactor is 2.6MPa, add 6.5ml methylcyclopentane, 200ml Containing 2.35g of ammonium persulfate aqueous solution to initiate the polymerization reaction, continue to feed the gas in the No. 2 reactor (vinylidene fluoride: tetrafluoroethylene: hexafluoropropylene = 65:20:15) to maintain the pressure of the reactor at 2.6MPa to keep the reaction After 3 hours of reaction, add 50ml of aqueous solution containing ammonium persulfate to the reaction kettle through the metering pump, and after continuing the reaction for 3 hours, stop adding the mixed gas, lower the temperature, and recover unreacted vinylidene fluoride, tetrafluoroethylene and hexafluoro Propylene monomer, put the material into the centrifuge through the discharge valve of the reactor, wash the material with hot deionized water several times after dehydration, and obtain the white fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 1500 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of vinylidene fluoride structural units in the fluororesin was 65.2%; the molar percentage of tetrafluoroethylene structural units was 19.8%; Min content is 15%.

Example 26: Emulsion polymerization, mixed gas feed, di-(2-ethylhexyl) phosphate ammonium salt as surfactant, oxidation-reduction reaction (ETFE)

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating and circulating cooling water, add 6L high-purity deionized water and 40.5g di-(2-ethylhexyl) phosphate to the reactor Ammonium, replaced by vacuum and nitrogen for three times, and the oxygen content was determined to be below 10ppm. Continue to vacuum until the pressure in the reactor is -0.1MPa, stir and heat up to 30°C, and the gas in the No. 1 gas mixer (ethylene: Tetrafluoroethylene=67:33) into the reactor until the pressure is 1.8MPa, then add 200ml of aqueous solution containing 1.5g of potassium persulfate and 1.2g of ammonium persulfate into the reactor with a metering pump, and wait until the temperature of the system is constant , add 9ml of methylcyclopentane to the reactor with a metering pump, 100ml of aqueous solution containing 0.45g of sodium sulfite and 0.76g of sodium metasulfite to initiate the reaction, and add the mixed gas of No. 2 mixed gas (ethylene: four Vinyl fluoride=49.5:50.5), and maintain the reaction pressure at 1.8MPa. Continue to feed No. 2 mixed gas to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.27g of sodium sulfite and 0.48g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 5 hours, stop adding the mixed gas and cool down. 1. Recover unreacted ethylene and tetrafluoroethylene monomers, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, and wash the material with hot deionized water several times after coagulation and dehydration to obtain white powder ETFE resin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2160 g of ETFE resin.

Elemental analysis, F19NMR, and IR analysis confirmed that the molar percentage of tetrafluoroethylene structural units in ETFE resin was 51.05%; the molar percentage of ethylene structural units was 48.95%.

Polymer data: The melt index of ETFE resin measured by the melt index meter is 6.5g/10mim (275°C, 2.16kg); the 1% weight decomposition temperature (Td) of the TGA test resin is 423.5°C; the DSC data shows that the melting point of the copolymer is at 259.9°C.

Embodiment 27: emulsion polymerization, mixed gas feed, di-(2-ethylhexyl) phosphate ammonium salt is surfactant, oxidation-reduction reaction (vinylidene fluoride-chlorotrifluoroethylene ethylene-hexafluoropropylene polymer )

Clean the 10L stainless steel autoclave equipped with mechanical stirring, temperature control device, circulating heating, and circulating cooling water, and add 6L high-purity deionized water and 50.5g of di-(2-ethylhexyl) phosphate to the reactor Ammonium, evacuate and replace with nitrogen for three times, measure the oxygen content below 10ppm, continue to evacuate until the pressure in the reactor is -0.1MPa, stir and heat up to 25°C, and the gas in the No. 1 gas mixer (bias fluoride Ethylene: Chlorotrifluoroethylene: Hexafluoropropylene=43:15:42) into the reactor until the pressure is 1.65MPa, then add 200ml of 1.5g of potassium persulfate and 1.2g of persulfuric acid into the reactor with a metering pump Ammonium aqueous solution, after the temperature of the system is constant, add 4.8ml methylcyclopentane to the reaction kettle with a metering pump, 100ml containing 0.45g sodium sulfite and 0.76g sodium metasulfite aqueous solution to initiate the reaction, and add 2 No. mixed gas (vinylidene fluoride: chlorotrifluoroethylene: hexafluoropropylene = 65:20:15), maintain the reaction pressure at 1.65MPa. Continue to feed No. 2 mixed gas to keep the reaction going. After 3 hours of reaction, add 50ml of aqueous solution containing 0.27g of sodium sulfite and 0.48g of sodium metasulfite to the reactor through a metering pump. After continuing to react for 5 hours, stop adding the mixed gas and cool down. , reclaim unreacted ethylene, chlorotrifluoroethylene and hexafluoropropylene monomer, put the white emulsion material into the coagulation bucket through the discharge valve of the reactor, wash the material with hot deionized water several times after coagulation and dehydration, and obtain White powder fluororesin. The product was further vacuum-dried at 100-120° C. for 8 hours to obtain 2160 g of fluororesin.

Elemental analysis, F19NMR, and IR analysis confirmed that the vinylidene fluoride structural unit in the fluororesin accounted for 64.9% by mole; the structural unit of chlorotrifluoroethylene accounted for 19.9%, and the structural unit of hexafluoropropylene The percentage content is 15.2%.

Claims (11)

1. the application of environment-friendly type tensio-active agent in fluoropolymer synthesis, is characterized in that described environment-friendly type tensio-active agent is selected from dialkyl phosphate salt and/or two-(2-ethylhexyl) phosphoric acid salt;

Described dialkyl phosphate salt has as, lower general structure (I):

Wherein: R is selected from the straight chained alkyl of C4 ~ C12, branched-chain alkyl or cycloalkyl, and M is selected from NH ₄ ⁺, Li ⁺, Na ⁺, K ⁺, Rb ⁺or Cs ⁺;

Described two-(2-ethylhexyl) phosphoric acid salt have following general structure (II):

Wherein: M is selected from NH ₄ ⁺, Li ⁺, Na ⁺, K ⁺, Rb ⁺or Cs ⁺;

Described fluoropolymer is selected from tetrafluoraoethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene, vinylidene-tetrafluoraoethylene-hexafluoropropylene copolymer or vinylidene-trifluorochloroethylene-hexafluoropropylene copolymer.

2., according to the application of environment-friendly type tensio-active agent according to claim 1 in fluoropolymer synthesis, it is characterized in that:

In described dialkyl phosphate salt, R is selected from n-butyl, hexyl or n-dodecyl, and M is selected from NH ⁴⁺, Na ⁺or K ⁺;

In described two-(2-ethylhexyl) phosphoric acid salt, M is selected from NH ₄ ⁺or Na ⁺;

The mass percent concentration of described environment-friendly type tensio-active agent in reaction medium is 0.01 ~ 5%;

Described fluoropolymer is selected from ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoro-ethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene or vinylidene-trifluorochloroethylene-hexafluoropropylene copolymer.

3. according to the application of environment-friendly type tensio-active agent according to claim 1 in fluoropolymer synthesis, it is characterized in that described fluoropolymer is ethylene-chlorotrifluoro-ethylene copolymer, under environment-friendly type tensio-active agent exists, carry out emulsion copolymerization by ethene and trifluorochloroethylene and react preparation, comprise the following steps:

(1) in reactor, add pure water and tensio-active agent, start reactor stirring at low speed, vacuumize and make in reactor that oxygen level is lower than 30ppm, the mass percent concentration of described tensio-active agent in reaction medium water is 2 ~ 5%;

(2) in reactor, add chain-transfer agent, described chain-transfer agent consumption is the 0.01-5% of reaction monomers ethene and trifluorochloroethylene monomer total mass;

(3) in reactor, part trifluorochloroethylene monomer and vinyl monomer is added, until reacting kettle inner pressure is 0.2 ~ 5MPa;

(4) intensification makes reactor temperature reach 10 ~ 120 DEG C, improve reactor mixing speed, in reactor, add initiator initiation reaction carry out, continue to add remaining trifluorochloroethylene monomer and vinyl monomer in reactor, keep reacting kettle inner pressure setting polymerization pressure ± 0.01MPa scope;

(5), after reaction terminates, namely emulsion material is obtained ethylene-chlorotrifluoro-ethylene copolymer after cohesion, washing and drying treatment.

4. according to the application of environment-friendly type tensio-active agent according to claim 1 in fluoropolymer synthesis, it is characterized in that described fluoropolymer is ethylene-chlorotrifluoro-ethylene copolymer, under environment-friendly type tensio-active agent exists, carry out suspension copolymerization preparation by ethene and trifluorochloroethylene, comprise the following steps:

(1) in reactor, add pure water and tensio-active agent, start reactor stirring at low speed, vacuumize and make in reactor that oxygen level is lower than 30ppm, the mass percent concentration of described tensio-active agent in reaction medium water is 0.01 ~ 2%;

(2) in reactor, add chain-transfer agent, described chain-transfer agent consumption is the 0.01-5% of reaction monomers ethene and trifluorochloroethylene monomer total mass;

(3) in reactor, part trifluorochloroethylene monomer and vinyl monomer is added, until reacting kettle inner pressure is 0.2 ~ 5MPa;

(4) intensification makes reactor temperature reach 10 ~ 120 DEG C, improve reactor mixing speed, in reactor, add initiator initiation reaction carry out, continue to add remaining trifluorochloroethylene monomer and vinyl monomer in reactor, keep reacting kettle inner pressure setting polymerization pressure ± 0.01MPa scope;

(5), after reaction terminates, namely ethylene-chlorotrifluoro-ethylene copolymer is obtained by after the washing of suspension pellet and drying treatment.

5., according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, it is characterized in that polymerization temperature is 10 ~ 120 DEG C, polymerization pressure is 0.2 ~ 5MPa.

6., according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, it is characterized in that described polymerization temperature is 20 ~ 70 DEG C, polymerization pressure is 0.5 ~ 3MPa.

7. according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, it is characterized in that initiator is Potassium Persulphate and/or ammonium persulphate, chain-transfer agent is selected from the one, two or three in methylene dichloride, trichloromethane and methylcyclopentane.

8., according to the application of environment-friendly type tensio-active agent according to claim 7 in fluoropolymer synthesis, it is characterized in that described initiator further containing sodium bisulfite and/or sodium metabisulphite.

9., according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, it is characterized in that described vinyl monomer and trifluorochloroethylene monomer can first mix and add reactor afterwards, also can add reactor separately independently; In described reactor, oxygen level is lower than 10ppm.

10. according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, the 1% weight decomposition temperature Td that it is characterized in that described ethylene-chlorotrifluoro-ethylene copolymer TGA is 380 ~ 450 DEG C, melting index is 0.1 ~ 50g/10mim (275 DEG C, 2.16kg).

11. according to the application of the environment-friendly type tensio-active agent described in claim 3 or 4 in fluoropolymer synthesis, it is characterized in that described ethylene-chlorotrifluoro-ethylene copolymer can further containing the one in following monomer, more than two or three combination: CF ₂=CF-CF ₃, CHF=CH-CF ₃, CH ₂=CF-CF ₃or CH ₂=CH-CF ₃.