CN116178598A - Tetrafluoroethylene-based polymer resin and preparation method thereof - Google Patents
Tetrafluoroethylene-based polymer resin and preparation method thereof Download PDFInfo
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- CN116178598A CN116178598A CN202210700597.5A CN202210700597A CN116178598A CN 116178598 A CN116178598 A CN 116178598A CN 202210700597 A CN202210700597 A CN 202210700597A CN 116178598 A CN116178598 A CN 116178598A
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- tetrafluoroethylene
- based polymer
- polymer resin
- monomer
- comonomer
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 35
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003999 initiator Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 69
- 239000000839 emulsion Substances 0.000 claims description 49
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 31
- 239000005977 Ethylene Substances 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- 239000001099 ammonium carbonate Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 claims description 2
- OIVQVBDAMYDDEM-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propoxy]propanoic acid Chemical compound OC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F OIVQVBDAMYDDEM-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 81
- 229920005989 resin Polymers 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000012986 chain transfer agent Substances 0.000 abstract description 11
- 239000006184 cosolvent Substances 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229920009441 perflouroethylene propylene Polymers 0.000 description 12
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229920002313 fluoropolymer Polymers 0.000 description 5
- 239000004811 fluoropolymer Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229960004624 perflexane Drugs 0.000 description 4
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the technical field of chemical materials, and particularly relates to tetrafluoroethylene-based polymer resin and a preparation method thereof. The tetrafluoroethylene-based polymer resin is prepared by polymerizing tetrafluoroethylene monomer and comonomer in the presence of hydrofluoroether, ammonium salt, initiator, dispersant and water. The tetrafluoroethylene-based polymer resin preparation raw material does not contain chain transfer agent, but the prepared resin has excellent performance, and the melting point and the melt index of the resin are equivalent to those of the resin prepared by using a cosolvent and chain transfer. The invention selects the hydrofluoroether auxiliary agent as the reaction raw material, does not need to additionally add chain transfer agents such as hydrogen, alkane or alcohols and the like in the process, effectively simplifies the preparation process, increases the operation safety, ensures that TFE monomers and other comonomers are easy to recycle, can be reused, and greatly reduces the production cost. In addition, the use amount of the hydrofluoroether auxiliary agent in the preparation process is less, the environment is protected, and the cost is further reduced.
Description
Technical Field
The invention belongs to the technical field of chemical materials, and particularly relates to tetrafluoroethylene-based polymer resin and a preparation method thereof.
Background
In the preparation of a copolymer synthesized by taking Tetrafluoroethylene (TFE) as a main monomer, if reactivity ratios of TFE and other comonomers are greatly different, a chain transfer agent is generally added into a polymerization system, and in order to increase the solubility of the monomers, fluorinated solvents such as fluorochlorohydrocarbon, perfluoroalkane, perfluorocycloalkane and the like, such as the preparation of fusible Polytetrafluoroethylene (PFA), the preparation of modified Fluorinated Ethylene Propylene (FEP) and the preparation of ethylene-tetrafluoroethylene copolymer (ETFE), are also added into the polymerization system.
PFA is a copolymer of tetrafluoroethylene and perfluoro-n-propyl vinyl ether (PPVE), which is a melt-processable polymer developed to improve the processability of polytetrafluoroethylene, and which can be melt-processed in addition to almost the same properties as polytetrafluoroethylene, and has important applications in the fields of chemical industry, semiconductors, etc.
For the preparation of PFA, the emulsion polymerization and suspension polymerization reactions are multipurpose, for the emulsion polymerization reaction, chain transfer agents are almost added into a reaction system because of the large reactivity ratio difference between TFE and PPVE monomers, and meanwhile, cosolvents are added into the system because of the small solubility of fluorine-containing monomers in water, so that the addition of the cosolvents not only increases the solubility of the monomers, but also plays roles of reducing the molecular weight distribution and improving the uniformity distribution of the comonomer on chain links. The emulsion preparation of PFA is described in patent US 3635926, wherein the chain transfer agent used is hydrogen, an alkane and a low molecular saturated monohydric alcohol and the cosolvent is the fluorochlorohydrocarbon trifluorotrichloroethane (F113). Currently, F113 has been disabled as a solvent, and in addition, hydrogen or alkane itself is a flammable and explosive gas, which presents a major safety hazard for the polymerization of TFE. More disadvantageous is that the use of hydrogen, during the process of recovering TFE after polymerization, TFE and hydrogen exist in the recovered gas, so that the recovery difficulty of TFE is too great, and many manufacturers even directly empty, so that the monomer cannot be recovered and utilized, thus the waste of TFE monomer can be caused, and the production cost is increased.
Patent CN109762091B discloses a process for the preparation of tetrafluoroethylene-based copolymers, wherein the co-solvent selected is perfluoroalkane or perfluorocycloalkane, which, although discarding forbidden F113, is additionally added with chain transfer agent, and the chain transfer agent used is hydrogen, alkane and alcohol, which still has the above mentioned problems.
In the preparation method of the Fluorinated Ethylene Propylene (FEP) disclosed in the patent CN 112358564A, the fluorinated ethylene propylene is prepared by taking perfluoroalkanes or perfluorocycloalkanes as cosolvent and simultaneously adding saturated alcohol, mercaptan or carbon tetrachloride and the like as chain transfer agents, and the method also introduces the chain transfer agents and the perfluoroalkanes at the same time, so that the process is complicated.
Patent CN 109721675B discloses a preparation method of ethylene-tetrafluoroethylene copolymer, which uses fluorine-containing solvent as solvent and uses 2-mercaptoethanol, cyclohexane or ethanol as chain transfer agent to prepare ethylene-tetrafluoroethylene (ETFE) copolymer, the method also uses fluorine-containing solvent and chain transfer agent, and the volume of fluorine-containing solvent is 70% -75% of the volume of the polymerization kettle, and the cost is high and the method is not environment-friendly.
In view of the foregoing, there is a great need for a safe, environmentally friendly process for preparing fluoropolymers that is easy to recover from the monomers.
Disclosure of Invention
Based on the above, the invention aims to provide a tetrafluoroethylene-based polymer resin which has excellent performance, and the preparation method is safe, simple, environment-friendly and convenient for monomer recovery.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
The tetrafluoroethylene-based polymer resin is prepared by polymerizing tetrafluoroethylene monomer and comonomer in the presence of hydrofluoroether, ammonium salt, initiator, dispersant and water;
the comonomer is at least one selected from perfluoroalkyl vinyl ether, ethylene and hexafluoropropylene; the general formula of the perfluoroalkyl vinyl ether is R f -O-CF＝CF 2 Wherein R is f Selected from perfluoroalkyl groups having 1 to 6 carbon atoms;
the mass ratio of the tetrafluoroethylene monomer to the comonomer to the hydrofluoroether to the ammonium salt to the initiator to the dispersing agent is 100: (1-50): (1-40): (0.1-5): (0.01-0.5): (0.1-5).
In some of these embodiments, the comonomer is selected from one or both of perfluoroalkyl vinyl ethers; the mass ratio of the comonomer to the tetrafluoroethylene monomer is (1-50): 100.
in some of these embodiments, the comonomer is selected from hexafluoropropylene and one of the perfluoroalkyl vinyl ethers; the mass ratio of the perfluoroalkyl vinyl ether to the tetrafluoroethylene monomer is (1-10): 100, wherein the mass ratio of hexafluoropropylene to tetrafluoroethylene monomer is (10-40): 100.
in some of these embodiments, the comonomer is selected from ethylene and hexafluoropropylene; the mass ratio of the ethylene to the tetrafluoroethylene monomer is (1-10): 100, wherein the mass ratio of hexafluoropropylene to tetrafluoroethylene monomer is (10-40): 100.
in some of these embodiments, the comonomer is selected from the group consisting of ethylene and one of the perfluoroalkyl vinyl ethers; the mass ratio of the perfluoroalkyl vinyl ether to the tetrafluoroethylene monomer is (2-10): 100, wherein the mass ratio of ethylene to tetrafluoroethylene monomer is (15-30): 100.
in some of these embodiments, the hydrofluoroether is selected from CF 3 CHFCF 2 OCH 2 CH 3 、CF 3 CHFCF 2 OCH 3 、CF 2 HCF 2 OCH 3 、CF 3 CH 2 OCF 2 CF 2 H、CF 2 HCF 2 OCH 2 CH 3 、CF 2 HCF 2 OCH 2 CF 2 CF 2 At least one of H.
In some embodiments, the ammonium salt is selected from at least one of ammonium bicarbonate, ammonium acetate, ammonium carbonate, ammonium oxalate, ammonium sulfite.
In some embodiments, the initiator is selected from at least one of potassium persulfate, ammonium persulfate, diisopropyl peroxydicarbonate, di-t-butyl peroxide, potassium persulfate-potassium hydrogen sulfite, and potassium permanganate-oxalic acid.
In some embodiments, the initiator is added in a single addition or multiple uniform additions in portions.
In some embodiments, the dispersant is selected from at least one of ammonium perfluorooctanoate, methylcellulose, perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid.
In some of these embodiments, the polymerization reaction is carried out at a temperature of 20℃to 120℃and a pressure of 1MPa to 6MPa.
In some of these embodiments, the polymerization reaction is carried out at a temperature of 40℃to 120℃and a pressure of 1MPa to 5MPa; further, the temperature is 60-120 ℃ and the pressure is 1-4 MPa; further, the temperature is 60-100 ℃ and the pressure is 1.5-4 MPa.
In some of these embodiments, the polymerization reaction time is 1h to 12h.
In some of these embodiments, the polymerization reaction time is 1h to 10h; further, the time is 1 to 8 hours; further, the time is 1h to 7h.
The invention also provides a preparation method of the tetrafluoroethylene-based polymer resin, which comprises the following steps: adding water, a dispersing agent and ammonium salt into a reaction system, vacuumizing, measuring the oxygen content, adding hydrofluoroether and comonomer into the reaction system by utilizing negative pressure after the oxygen content is qualified, heating, adding an initiator, and continuously adding tetrafluoroethylene monomer or a mixture of tetrafluoroethylene monomer and comonomer at the same time, keeping the pressure of the reaction system stable, and carrying out reaction; and after the reaction is finished, cooling and discharging to obtain emulsion, and then condensing, washing and drying the emulsion to obtain the tetrafluoroethylene-based polymer resin.
In some of these embodiments, the emulsion has a solids content of 15wt% to 40wt%.
In some of these embodiments, the emulsion has a solids content of 15wt% to 35wt%; further, the emulsion has a solids content of 15wt% to 30wt%.
In some of these embodiments, the elevated temperature is 20 ℃ to 120 ℃; further, the temperature is 40-120 ℃; further, the temperature is 60 ℃ to 120 ℃.
In some of these embodiments, the pressure is 1MPa to 6MPa; further, the pressure is 1MPa to 5MPa; further, the pressure is 1.5MPa to 4MPa.
In some of these embodiments, the reaction time is 1h to 12h; further, the time is 1 h-10 h; further, the time is 1 to 8 hours.
Compared with the prior art, the invention has the following beneficial effects:
the inventor finds that the hydrofluoroether auxiliary agent can be used as a cosolvent and a chain transfer agent simultaneously when being used for preparing the tetrafluoroethylene-based polymer through a great deal of researches, and further compounds the hydrofluoroether auxiliary agent with proper raw materials to obtain the tetrafluoroethylene-based polymer resin in an optimized way. The raw materials for preparing the tetrafluoroethylene-based polymer resin do not contain chain transfer agents such as hydrogen, alkane, alcohols and the like, but the prepared resin has excellent performance, and the melting point and the melt index of the resin are equivalent to those of the resin prepared by using a cosolvent and chain transfer.
The invention effectively simplifies the preparation process of the tetrafluoroethylene-based polymer resin, increases the operation safety, ensures that TFE monomers and other comonomers are easier to recycle and can be reused, and greatly reduces the production cost. In addition, the use amount of the hydrofluoroether auxiliary agent is less after the formula is optimized, the environment is protected, and the cost is further reduced.
Detailed Description
The experimental methods of the present invention, in which specific conditions are not specified in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The various chemicals commonly used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having" and any variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to the elements or modules listed but may alternatively include additional steps not listed or inherent to such process, method, article, or device.
The following description of the embodiments of the present invention will be made more apparent and fully by reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The embodiment provides a tetrafluoroethylene-based polymer resin, which is prepared by polymerizing tetrafluoroethylene monomer and comonomer in the presence of hydrofluoroether, ammonium salt, initiator, dispersant and water;
the comonomer is at least one selected from perfluoroalkyl vinyl ether, ethylene and hexafluoropropylene; the general formula of the perfluoroalkyl vinyl ether is R f -O-CF＝CF 2 Wherein R is f Selected from perfluoroalkyl groups having 1 to 6 carbon atoms;
the mass ratio of the tetrafluoroethylene monomer to the comonomer to the hydrofluoroether to the ammonium salt to the initiator to the dispersing agent is 100: (1-50): (1-40): (0.1-5): (0.01-0.5): (0.1-5).
In some preferred embodiments, the mass ratio of tetrafluoroethylene monomer, comonomer, hydrofluoroether, ammonium salt, initiator and dispersant is 100: (1-50): (5-30): (0.5-5): (0.05-0.5): (0.1-3.5).
More preferably, the mass ratio of the tetrafluoroethylene monomer, the comonomer, the hydrofluoroether, the ammonium salt, the initiator and the dispersing agent is 100: (7.5 to 45): (7.5-25): (0.5-5): (0.1-0.4): (0.5-3).
Specifically, the mass ratio of the comonomer to the tetrafluoroethylene monomer is 1: 100. 2: 100. 3: 100. 5: 100. 7.5: 100. 10: 100. 12: 100. 17: 100. 20: 100. 23: 100. 25.5: 100. 30: 100. 32.5: 100. 38: 100. 40:100. 42.5: 100. 45: 100. 47: 100. 50:100.
specifically, the mass ratio of the hydrofluoroether to the tetrafluoroethylene monomer is 1: 100. 3.5: 100. 5: 100. 7.5: 100. 10: 100. 12.5: 100. 16.7: 100. 20: 100. 22.5: 100. 25: 100. 27.5: 100. 30: 100. 32.5: 100. 35: 100. 37: 100. 38.5: 100. 40:100.
in some embodiments, the perfluoroalkyl vinyl ether is selected from at least one of perfluoro-n-propyl vinyl ether and perfluoroethyl vinyl ether.
Another embodiment of the present invention provides a method for preparing the tetrafluoroethylene-based polymer resin as described above.
In some embodiments, the tetrafluoroethylene-based polymer resin is a PFA or modified PTFE product, and the method of making comprises the steps of: adding water, a dispersing agent and ammonium salt into a reaction system, vacuumizing, measuring the oxygen content, adding hydrofluoroether and a comonomer into the reaction system by utilizing negative pressure after the oxygen content is qualified, heating, adding an initiator, and continuously adding tetrafluoroethylene monomer at the same time, keeping the pressure of the reaction system stable, and carrying out reaction; and after the reaction is finished, cooling and discharging to obtain emulsion, and then condensing, washing and drying the emulsion to obtain the tetrafluoroethylene-based polymer resin.
In some embodiments, the tetrafluoroethylene-based polymer resin is a modified FEP or modified ETFE product, and the method of making comprises the steps of: adding water, a dispersing agent and ammonium salt into a reaction system, vacuumizing, measuring the oxygen content, adding hydrofluoroether and comonomer into the reaction system by utilizing negative pressure after the oxygen content is qualified, heating, adding an initiator, simultaneously pumping the mixed monomer in an initial tank into a polymerization kettle to the polymerization pressure by a compressor, (the mixed monomer in the initial tank comprises the combination of TFE and HFP or the combination of TFE and ethylene or the combination of TFE, HFP and ethylene) after the polymerization reaction starts, pumping additional monomer by a compressor, (the additional monomer comprises the mixed monomer of TFE and HFP or the mixed monomer of TFE and ethylene or the mixed monomer of TFE, HFP and ethylene) and keeping the pressure of the reaction system and the reaction temperature unchanged, reacting until the specified amount of the mixed monomer is put into, cooling and discharging to obtain emulsion, testing the solid content of the emulsion, and then condensing, washing and drying the emulsion to obtain the tetrafluoroethylene-based polymer resin.
Example 1
The embodiment provides a preparation method of tetrafluoroethylene-based polymer resin, which comprises the following steps:
adding 60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane carboxylic acid ammonium and 106g of ammonium carbonate into a 100L polymerization kettle, vacuumizing the polymerization kettle, measuring the oxygen content, and using negative pressure to carry out 4kg of CF after the oxygen content is qualified 2 HCF 2 OCH 2 CH 3 And sucking 720g of PPVE into a polymerization kettle, heating to 70 ℃, pumping 1600g of potassium persulfate initiator with mass fraction of 3% into the polymerization kettle within 30min, continuously introducing TFE monomer, keeping the system pressure at 2.1Mpa, stopping the reaction after 120min of polymerization, cooling the polymerization kettle, recovering 1kg of unreacted TFE monomer, and removing impurities from the recovered TFE monomer and drying for recycling. The TFE monomer to be reacted was measured at 20kg, the resulting emulsion was discharged and the solid content of the emulsion was measured, and then the emulsion was coagulated, washed and dried to obtain a fluoropolymer resin.
Example 2
The embodiment provides a preparation method of tetrafluoroethylene-based polymer resin, which comprises the following steps:
into a 100L polymerizer was charged 60L of water and 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane ammonium carboxylate and 106g ammonium carbonate, then vacuumizing the polymerization kettle, measuring the oxygen content, and after the oxygen content is qualified, using negative pressure to carry out CF of 3.6kg 2 HCF 2 OCH 2 CH 3 And 180g of PPVE is sucked into a polymerization kettle, then a certain amount of initial monomer (the proportion of tetrafluoroethylene and hexafluoropropylene in the initial monomer is 18wt%:82 wt%) is pumped into the polymerization kettle from the initial tank through a compressor, 1600g of ammonium persulfate initiator with the mass fraction of 3% is pumped into the polymerization kettle in 30min when the temperature is raised to 99 ℃, the additional monomer is added into the polymerization kettle through the compressor, the proportion of tetrafluoroethylene and hexafluoropropylene in the additional monomer is 89wt%:11wt%, the pressure of the system is kept to be 3.5Mpa, the reaction is stopped after the reaction amount of the additional monomer reaches a specified value, the polymerization time is 185min, then the polymerization kettle is cooled, the unreacted TFE and HFP monomers are recovered, the mass of the TFE and HFP monomers is calculated to be 1.2kg, and the recovered TFE and HFP monomers can be recycled through impurity removal and drying. The consumption of TFE and HFP monomers was determined to be 19kg, the resulting emulsion was let down and the solids content of the emulsion was checked, and then the emulsion was coagulated, washed and dried to give a FEP resin modified with PPVE.
Example 3
The embodiment provides a preparation method of tetrafluoroethylene-based polymer resin, which comprises the following steps:
adding 60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane carboxylic acid ammonium and 100g of ammonium carbonate into a 100L polymerization kettle, vacuumizing the polymerization kettle, measuring the oxygen content, and using negative pressure to cool 3.6kg of CF after the oxygen content is qualified 2 HCF 2 OCH 2 CH 3 Sucking into a polymerization kettle, then pumping quantitative initial monomers (the proportion of ethylene monomer, tetrafluoroethylene and hexafluoropropylene in the initial monomers is 12 percent by weight and 80 percent by weight) into the polymerization kettle from the initial tank through a compressor, pumping 1600g of ammonium persulfate initiator with the mass fraction of 3 percent into the polymerization kettle within 30min when the temperature is raised to 99 ℃, adding additional monomers into the polymerization kettle through the compressor, the proportion of ethylene, tetrafluoroethylene and hexafluoropropylene in the additional monomers is 2 percent by weight and 88 percent by weight and 10 percent by weight, maintaining the system pressure to be 3.65Mpa, stopping the reaction when the reaction quantity of the additional monomers reaches a specified value, polymerizing for 196min, and then polymerizingAnd cooling the reactor, recovering unreacted ethylene, TFE and HFP monomers, calculating the mass of the recovered monomers to be 1.1kg, removing impurities and drying the recovered ethylene monomers, TFE and HFP monomers to recycle, discharging the obtained emulsion, detecting the solid content of the emulsion, and condensing, washing and drying the emulsion to obtain the FEP resin modified by ethylene.
Example 4
The embodiment provides a preparation method of tetrafluoroethylene-based polymer resin, which comprises the following steps:
adding 60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane carboxylic acid ammonium and 120g of ammonium oxalate into a 100L polymerization kettle, vacuumizing the polymerization kettle, measuring the oxygen content, and using negative pressure to cool 2.4kg of CF after the oxygen content is qualified 2 HCF 2 OCH 2 CH 3 And 240g of PPVE is sucked into the polymerization kettle, then a certain amount of initial monomer (15 wt% of ethylene monomer and 85wt% of tetrafluoroethylene in the initial monomer) is pumped into the polymerization kettle from the initial tank through a compressor, 4800g of sodium bisulfite solution with the mass fraction of 3wt% is firstly added into the polymerization kettle when the temperature is raised to 54 ℃, and then 2wt% of potassium persulfate solution with the mass fraction of 1600g is uniformly added into the polymerization kettle, so that the potassium persulfate solution is ensured to be added within 3 hours, and the additional monomer is added into the polymerization kettle by the compressor while the adding of the potassium persulfate solution is started, wherein the proportion of ethylene and tetrafluoroethylene in the additional monomer is 21wt%:79wt% maintaining the pressure of the system at 2.4MPa, stopping the reaction after the reaction amount of the additional monomer reaches a specified value, allowing the polymerization time to reach 320min, cooling the polymerization kettle, recovering unreacted ethylene and TFE monomer, calculating the mass of the recovered monomer to be 1kg, discharging the obtained emulsion, detecting the solid content of the emulsion, and condensing, washing and drying the emulsion to obtain the ETFE resin.
Comparative example 1
80L of water, 620g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane carboxylic acid ammonium and 100g of ammonium carbonate are added into a 100L polymerization kettle, then the polymerization kettle is vacuumized, the oxygen content is detected, after the oxygen content is qualified, 4kg of perfluorohexane and 720g of PPVE are sucked into the polymerization kettle by utilizing negative pressure, and meanwhile, 0.6MPa of hydrogen is introduced into the kettle. When the temperature is raised to 70 ℃, 1600g of potassium persulfate initiator with mass fraction of 3% is pumped into a polymerization kettle within 30min, meanwhile, TFE monomer is continuously pumped, the system pressure is kept at 2.1Mpa, the reaction is stopped after 120min of polymerization, the polymerization kettle is cooled, unreacted TFE monomer and hydrogen are recovered, the mass of the unreacted TFE monomer is calculated to be 1.1kg, the gas chromatographic analysis is carried out, the TFE content in the mixed gas is 98.7%, the consumption of the TFE monomer is measured to be 20kg, the emulsion obtained by discharging is detected, the solid content of the emulsion is detected, and then the emulsion is coagulated, washed and dried to obtain the fluorine-containing polymer resin.
In this comparative example, the recovered TFE monomer cannot be recycled because it contains hydrogen, and TFE and hydrogen are difficult to separate, and direct vent treatment is generally selected, which corresponds to about 1.1kg of TFE feedstock being wasted.
Comparative example 2
Adding 60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonylammonium carboxylate and 106g of ammonium carbonate into a 100L polymerization kettle, vacuumizing the polymerization kettle, measuring the oxygen content, sucking 3.6kg of perfluorohexane and 180g of PPVE into the polymerization kettle by using negative pressure after the oxygen content is qualified, simultaneously introducing 30g of ethane into the kettle, adding quantitative initial monomers (the ratio of tetrafluoroethylene to hexafluoropropylene in the initial monomers is 18wt%:82 wt%) from an initial tank, heating to 99 ℃, adding 1600g of ammonium persulfate initiator with the mass fraction of 3% into the polymerization kettle in 30min, adding additional monomers into the polymerization kettle by using a compressor, stopping the reaction after the reaction amount of the additional monomers reaches a specified value, cooling the polymerization kettle, recovering unreacted TFE, HFP and ethane gas, calculating the mass of TFE, HFP and HFP to be 1.2kg, detecting the mass of TFP and PPP, and drying the emulsion, and detecting the emulsion, and the emulsion is the emulsion, and the emulsion is modified, and the emulsion is obtained, the emulsion is washed, and the emulsion is subjected to the emulsion is 19, and the emulsion is subjected to the emulsion is obtained.
In this comparative example, the recovered TFE and HFP monomers cannot be recycled because they contain ethane and TFE and HFP are difficult to separate, and direct vent processing is generally selected, which amounts to about 1.2kg of TFE feedstock being wasted.
Comparative example 3
60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane carboxylic acid ammonium and 106g of ammonium carbonate are added into a 100L polymerization kettle, then the polymerization kettle is vacuumized, the oxygen content is measured, after the oxygen content is qualified, 3.6kg of perfluorohexane is sucked into the polymerization kettle by utilizing negative pressure, 30g of ethane is simultaneously introduced into the kettle, and then quantitative initial monomers (the proportion of ethylene monomer, tetrafluoroethylene and hexafluoropropylene in the initial monomers is 12 wt%) are injected into the initial tank by a compressor: 8wt percent to 80wt percent), heating to 99 ℃, pumping 1600g of ammonium persulfate initiator with the mass fraction of 3 percent into a polymerization kettle within 30min, pumping additional monomer into the polymerization kettle by a compressor, wherein the proportion of ethylene, tetrafluoroethylene and hexafluoropropylene in the additional monomer is 2wt percent to 10wt percent, maintaining the pressure of the system to be 3.65Mpa, stopping the reaction after the reaction quantity of the additional monomer reaches a specified value, polymerizing for 196min, cooling the polymerization kettle, recovering unreacted ethylene, TFE and HFP monomers, calculating the mass of the recovered monomers to be 1.2kg, the total amount of the reacted ethylene monomers, TFE and HFP monomers to be 19kg, discharging the obtained emulsion, detecting the solid content of the emulsion, and condensing, washing and drying the emulsion to obtain the FEP resin modified by ethylene.
In this comparative example, the recovered TFE and HFP monomers cannot be recycled because they contain ethane and TFE and HFP are difficult to separate, and direct vent processing is generally selected, which amounts to about 1.2kg of TFE feedstock being wasted.
Comparative example 4
Adding 60L of water, 600g of perfluoro-2, 5-dimethyl-3, 6-dioxanonane ammonium carboxylate and 120g of ammonium oxalate into a 100L polymerization kettle, vacuumizing the polymerization kettle, measuring the oxygen content, sucking 2.4kg of perfluorohexane and 240g of PPVE into the polymerization kettle by using negative pressure after the oxygen content is qualified, simultaneously introducing 44g of propane into the polymerization kettle, then adding quantitative initial monomers (15 wt% of ethylene monomer and 85wt% of tetrafluoroethylene in the initial monomers) into the initial tank by a compressor, heating to 54 ℃, adding 4800g of sodium bisulfate solution with the mass fraction of 3wt% into the polymerization kettle, uniformly adding potassium persulfate solution with the mass fraction of 2wt% into the polymerization kettle, wherein the total amount of the potassium persulfate solution is 1600g, ensuring that the potassium persulfate solution is added within 3 hours, adding the additional monomers into the polymerization kettle by a compressor, and adding the ethylene and the tetrafluoroethylene in the additional monomers into the polymerization kettle with the proportion of 21%:79wt% maintaining the pressure of the system at 2.4MPa, stopping the reaction after the reaction amount of the additional monomer reaches a specified value, allowing the polymerization time to reach 360min, cooling the polymerization kettle, recovering unreacted ethylene and TFE monomer, calculating the mass of the recovered monomer to be 1kg, discharging the obtained emulsion, detecting the solid content of the emulsion, and condensing, washing and drying the emulsion to obtain the ETFE resin.
In this comparative example, the recovered TFE and ethylene monomers cannot be recycled because propane is contained, and it is difficult to separate propane from TFE and ethylene, and direct vent treatment is generally selected, which corresponds to about 1kg of TFE raw material being wasted.
The emulsions prepared in examples 1 to 4 and comparative examples 1 to 4 were tested for the solid content and the properties of the fluoropolymer resin.
The testing method comprises the following steps:
1. emulsion solids content: the emulsion solids content was determined according to the GB1725-1979 paint solids content determination method.
2. Melting point: melting points of ETFE and FEP were tested according to ASTM D3418: taking 5mg of ETFE or FEP sample, placing the sample into a sample pool, heating the sample from 100 ℃ to 300 ℃ at the speed of 10 ℃/min, and recording the change of a curve, wherein the highest point of a secondary melting peak is the melting point of the ETFE or FEP; melting point of PFA was tested according to ASTM D4591: taking 5mg of PFA sample, placing the sample into a sample tank, heating the sample from 100 ℃ to 350 ℃ at the speed of 10 ℃/min, recording the change of a curve, and obtaining the highest point of a secondary melting peak as the melting point of the PFA.
3. Melt index: melt indices of FEP and PFA were tested according to ASTM2116, test conditions: a 5kg weight, the test temperature is 372 ℃; melt index of ETFE was tested according to international standard ASTM-1238, test conditions: the load was a 5kg weight and the temperature was 297 ℃.
Test results:
the results are shown in Table 1:
TABLE 1 Performance test results
As can be seen from the data in Table 1, the fluoropolymer resins produced according to the present invention (examples 1-4) have excellent properties. As is clear from comparative examples 1 to 4 and comparative examples 1 to 4, in the present invention, when other raw materials and reaction conditions are the same, only the cosolvent hydrofluoroether is added but the chain transfer agent is not used, and comparative documents 1 to 4 use the cosolvent and hydrogen, ethane or propane as the chain transfer agent at the same time, but the properties of the fluoropolymer resin obtained by the two are almost the same. The hydrofluoroether used in the invention has the functions of a cosolvent and a chain transfer agent, so that the preparation process of the invention has better safety, the monomer is easy to recycle, and the production cost is reduced.
The invention has been further described with reference to specific embodiments, but it should be understood that the detailed description is not to be construed as limiting the spirit and scope of the invention, but rather as providing those skilled in the art with the benefit of this disclosure with the benefit of their various modifications to the described embodiments.
Claims (10)
1. The tetrafluoroethylene-based polymer resin is characterized by being prepared by polymerizing tetrafluoroethylene monomer and comonomer in the presence of hydrofluoroether, ammonium salt, initiator, dispersant and water;
the comonomer is at least one selected from perfluoroalkyl vinyl ether, ethylene and hexafluoropropylene; the general formula of the perfluoroalkyl vinyl ether is R f -O-CF＝CF 2 Wherein R is f Selected from perfluoroalkyl groups having 1 to 6 carbon atoms；
The mass ratio of the tetrafluoroethylene monomer to the comonomer to the hydrofluoroether to the ammonium salt to the initiator to the dispersing agent is 100: (1-50): (1-40): (0.1-5): (0.01-0.5): (0.1-5).
2. The tetrafluoroethylene-based polymer resin according to claim 1, wherein the comonomer is selected from one or both of perfluoroalkyl vinyl ethers; the mass ratio of the comonomer to the tetrafluoroethylene monomer is (1-50): 100.
3. the tetrafluoroethylene-based polymer resin according to claim 1, wherein the comonomer is selected from hexafluoropropylene and one of perfluoroalkyl vinyl ethers; the mass ratio of the perfluoroalkyl vinyl ether to the tetrafluoroethylene monomer is (1-10): 100, wherein the mass ratio of hexafluoropropylene to tetrafluoroethylene monomer is (10-40): 100.
4. the tetrafluoroethylene-based polymer resin according to claim 1, wherein the comonomer is selected from the group consisting of ethylene and hexafluoropropylene; the mass ratio of the ethylene to the tetrafluoroethylene monomer is (1-10): 100, wherein the mass ratio of hexafluoropropylene to tetrafluoroethylene monomer is (10-40): 100.
5. the tetrafluoroethylene-based polymer resin according to claim 1, wherein the comonomer is selected from one of perfluoroalkyl vinyl ethers and ethylene; the mass ratio of the perfluoroalkyl vinyl ether to the tetrafluoroethylene monomer is (2-10): 100, wherein the mass ratio of ethylene to tetrafluoroethylene monomer is (15-30): 100.
6. the tetrafluoroethylene-based polymer resin according to claim 1, wherein the hydrofluoroether is selected from the group consisting of CF 3 CHFCF 2 OCH 2 CH 3 、CF 3 CHFCF 2 OCH 3 、CF 2 HCF 2 OCH 3 、CF 3 CH 2 OCF 2 CF 2 H、CF 2 HCF 2 OCH 2 CH 3 、CF 2 HCF 2 OCH 2 CF 2 CF 2 At least one of H.
7. The tetrafluoroethylene-based polymer resin according to claim 1, wherein the ammonium salt is at least one selected from the group consisting of ammonium bicarbonate, ammonium acetate, ammonium carbonate, ammonium oxalate and ammonium sulfite; and/or the number of the groups of groups,
the initiator is at least one selected from potassium persulfate, ammonium persulfate, diisopropyl peroxydicarbonate, di-tert-butyl peroxide, potassium persulfate-potassium hydrogen sulfite and potassium permanganate-oxalic acid; and/or the number of the groups of groups,
the dispersing agent is at least one selected from ammonium perfluorooctanoate, methyl cellulose and perfluoro-2, 5-dimethyl-3, 6-dioxanonanoic acid.
8. The tetrafluoroethylene-based polymer resin according to claim 1, wherein the polymerization reaction is carried out at a temperature of 20℃to 120℃and a pressure of 1MPa to 6MPa.
9. The method for producing a tetrafluoroethylene-based polymer resin according to any one of claims 1 to 8, comprising the steps of: adding water, a dispersing agent and ammonium salt into a reaction system, vacuumizing, measuring the oxygen content, adding hydrofluoroether and comonomer into the reaction system by utilizing negative pressure after the oxygen content is qualified, heating, adding an initiator, and continuously adding tetrafluoroethylene monomer or a mixture of tetrafluoroethylene monomer and comonomer at the same time, keeping the pressure of the reaction system stable, and carrying out reaction; and after the reaction is finished, cooling and discharging to obtain emulsion, and then condensing, washing and drying the emulsion to obtain the tetrafluoroethylene-based polymer resin.
10. The method of preparing a tetrafluoroethylene-based polymer resin according to claim 9, wherein the emulsion has a solid content of 15wt% to 40wt%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328579A (en) * | 1998-11-30 | 2001-12-26 | 纳幕尔杜邦公司 | Fluoromonomer polymerization |
| CN1708519A (en) * | 2002-10-31 | 2005-12-14 | 3M创新有限公司 | Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin |
| JP2011032363A (en) * | 2009-07-31 | 2011-02-17 | Asahi Glass Co Ltd | Method for producing fluorine-containing copolymer |
| CN109721892A (en) * | 2017-10-27 | 2019-05-07 | 中昊晨光化工研究院有限公司 | Vinylidene thermoplastic resin of low-gel content and its preparation method and application |
| CN113260660A (en) * | 2018-12-27 | 2021-08-13 | Ａｇｃ株式会社 | Method for producing particles and method for producing molded body |
-
2022
- 2022-06-20 CN CN202210700597.5A patent/CN116178598A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328579A (en) * | 1998-11-30 | 2001-12-26 | 纳幕尔杜邦公司 | Fluoromonomer polymerization |
| CN1708519A (en) * | 2002-10-31 | 2005-12-14 | 3M创新有限公司 | Emulsifier free aqueous emulsion polymerization to produce copolymers of a fluorinated olefin and hydrocarbon olefin |
| JP2011032363A (en) * | 2009-07-31 | 2011-02-17 | Asahi Glass Co Ltd | Method for producing fluorine-containing copolymer |
| CN109721892A (en) * | 2017-10-27 | 2019-05-07 | 中昊晨光化工研究院有限公司 | Vinylidene thermoplastic resin of low-gel content and its preparation method and application |
| CN113260660A (en) * | 2018-12-27 | 2021-08-13 | Ａｇｃ株式会社 | Method for producing particles and method for producing molded body |
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