CN115073640A - Preparation method of ethylene-tetrafluoroethylene copolymer - Google Patents
Preparation method of ethylene-tetrafluoroethylene copolymer Download PDFInfo
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- CN115073640A CN115073640A CN202210802604.2A CN202210802604A CN115073640A CN 115073640 A CN115073640 A CN 115073640A CN 202210802604 A CN202210802604 A CN 202210802604A CN 115073640 A CN115073640 A CN 115073640A
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- ethylene
- tetrafluoroethylene
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- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 36
- -1 ethylene-tetrafluoroethylene Chemical group 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- LXANZHXWGZWFAC-UHFFFAOYSA-N 2,3-dichloro-1,1,1,2,3,4,4,4-octafluorobutane Chemical compound FC(F)(F)C(F)(Cl)C(F)(Cl)C(F)(F)F LXANZHXWGZWFAC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 72
- 239000005977 Ethylene Substances 0.000 claims description 51
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 49
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 22
- 238000007334 copolymerization reaction Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 14
- 239000012986 chain transfer agent Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 11
- 238000007872 degassing Methods 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 claims description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- WWVMHGUBIOZASN-UHFFFAOYSA-N 1-methyl-3-prop-2-enylimidazol-1-ium Chemical compound CN1C=C[N+](CC=C)=C1 WWVMHGUBIOZASN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 2
- 238000010792 warming Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- FXPHNQAHHHWMAV-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)OC=C FXPHNQAHHHWMAV-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 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 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- FQTUOJOWQBMFTM-UHFFFAOYSA-N 1-butyl-3-ethenyl-2h-imidazole Chemical compound CCCCN1CN(C=C)C=C1 FQTUOJOWQBMFTM-UHFFFAOYSA-N 0.000 description 1
- UVQPDGXQIPNYNU-UHFFFAOYSA-N 1-ethenyl-3-ethyl-2h-imidazole Chemical compound CCN1CN(C=C)C=C1 UVQPDGXQIPNYNU-UHFFFAOYSA-N 0.000 description 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a preparation method of an ethylene-tetrafluoroethylene copolymer, which uses an environment-friendly organic solvent 2, 3-dichlorooctafluorobutane as a reaction medium, wherein the organic solvent has low ozone consumption potential and global warming potential, can be recycled after impurity removal after the reaction is finished, and has the advantages of low solvent loss, environmental protection and high economic benefit; the ethylene-tetrafluoroethylene resin prepared by the method has excellent mechanical property and has excellent market prospect in industrial production.
Description
Technical Field
The invention relates to the field of high molecular polymerization, in particular to a preparation method of an ethylene-tetrafluoroethylene copolymer.
Background
The ethylene-tetrafluoroethylene copolymer is a chemical substance, ETFE is the toughest fluoroplastic, the good heat resistance, chemical resistance and electrical insulation performance of PTFE are kept, meanwhile, the radiation resistance and mechanical performance are improved to a great extent, and the tensile strength can reach 50MPa, which is 2 times that of polytetrafluoroethylene.
CN110467695B discloses a preparation method of an ethylene-tetrafluoroethylene copolymer, which is mainly improved in that in the process of preparing the ethylene-tetrafluoroethylene copolymer by using ethylene and tetrafluoroethylene as raw materials through an emulsion polymerization method, a mixed solution of water and an organic solvent is used as a reaction medium, and polymerization reaction is carried out under the action of a redox mixed initiator, wherein the temperature of the polymerization reaction is 40-55 ℃; and after the polymerization reaction is finished, sintering the obtained polymer at the temperature of 320-350 ℃ to obtain the polymer. The ETFE resin prepared by the method has good thermal stability in the processing and application processes, the melting point is 240-275 ℃, the tensile strength is about 40-52 MPa, and the elongation at break is 300%.
CN104151754A discloses a high-flowability ETFE copolymer composition and a preparation method thereof. The composition comprises a first ETFE component and a second ETFE component, the first and second ETFE components having substantially the same composition but different molecular weights, comprising: ethylene repeating unit A, tetrafluoroethylene repeating unit B and other repeating unit C copolymerizable with ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene repeating unit A to the tetrafluoroethylene repeating unit B is from 40/60 to 40/60; the amount of the other repeating units C is 0.1 to 5.0 mol% based on the total number of moles of the ethylene repeating unit A and the tetrafluoroethylene repeating unit B; the melt flow index of the composition is 15-150g/10min at 297 ℃ under the condition of 5 kg; the ethylene-tetrafluoroethylene copolymer resin composition has two melting points, wherein the first melting point is 233 ℃ and the second melting point is 245 ℃ and 275 ℃.
JP2006332642 provides an ethylene/tetrafluoroethylene copolymer having excellent heat resistance and a method for producing the same. An ethylene/tetrafluoroethylene copolymer is produced by polymerizing ethylene and tetrafluoroethylene in a chlorine atom-free organic solvent as a polymerization medium in the presence of a chlorine atom-free chain transfer agent and a chlorine atom-free polymerization initiator and in the substantial absence of a chain transfer compound having a carbon-chlorine atom bond in the reaction system.
At present, the ETFE polymerization process usually uses an organic solvent as a medium and peroxide as an initiator to carry out free radical copolymerization of TFE, ethylene and special fluorine-containing olefin in a solution precipitation polymerization manner.
However, the Montreal convention has made strict regulations on the production of Pentay chlorofluorocarbons such as CFC-11, CFC-12, CFC-113, CFC-114, CFC-115, and Sanhalon. The fluorine-containing organic solvent which is currently used, for example, 1, 2-trifluorotrichloroethane (R113) or the like is contained therein. Therefore, there is a need to find suitable environmentally friendly organic solvents for replacing solvents with higher greenhouse effect and ozone destruction capability.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of an ethylene-tetrafluoroethylene copolymer, belonging to the field of high polymer polymerization
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 500-600 parts of organic solvent, 2-8 parts of liquid-phase monomer and 0.3-2.4 parts of chain transfer agent into a polymerization kettle according to parts by weight, starting stirring, wherein the stirring speed is 60-120rpm, heating the polymerization kettle to the reaction temperature, introducing first mixed gas of ethylene and tetrafluoroethylene to the pressure of the polymerization kettle to the reaction pressure, and adding 0.01-0.1 part of initiator to initiate copolymerization.
S2: and (3) after the polymerization reaction starts, introducing a second mixed gas of ethylene and tetrafluoroethylene, maintaining the pressure of the polymerization kettle, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 45-85 parts, discharging the pressure of the polymerization kettle, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
According to the method provided by the invention, the organic solvent is selected from 2, 3-dichlorooctafluorobutane, and the solvent can enter a solvent storage tank after being recovered and separated after the reaction is finished and can be recycled.
According to the method provided by the invention, the liquid-phase monomer is one or more of perfluoroalkyl ethylene, perfluoroalkyl vinyl ether, hexafluoropropylene and hexafluoroisobutylene.
According to the method provided by the invention, the chain transfer agent is selected from one or more mixtures of alcohols, esters, ethers, ketones, alkanes and aromatic hydrocarbons.
According to the method provided by the invention, the initiator is selected from one or more mixtures of peroxyalcohol, peroxyacid, peroxyester, peroxyacyl, azo compound, persulfate, perchlorate, permanganate and the like.
According to the process provided by the present invention, the molar ratio of ethylene to tetrafluoroethylene in the first mixture is 1: 2 to 8.
According to the process provided by the present invention, the molar ratio of ethylene to tetrafluoroethylene in the second mixture is 1: 0.5 to 2.0.
According to the method provided by the invention, the polymerization temperature is 45-85 ℃.
According to the method provided by the invention, the polymerization pressure is 1200-1600 kPa.
According to the method provided by the invention, 0.001-0.01 part of alkenyl ionic liquid and 0.0001-0.01 part of vinyl ferrocene can be added into S1 to participate in the reaction.
According to the method provided by the invention, the alkenyl ionic liquid comprises vinyl and allyl ionic liquids.
According to the method provided by the invention, the alkenyl ionic liquid cation comprises three main groups of 1-vinyl-3-alkyl imidazole, 1-allyl-3-vinyl imidazole and the like, wherein alkyl groups comprise methyl, ethyl, butyl and the like.
According to the method provided by the invention, the alkenyl ionic liquid anion comprises chlorine, bromine, tetrafluoroboric acid, hexafluorophosphoric acid, bis (trifluoromethanesulfonyl) imide and the like.
According to the method provided by the invention, the alkenyl ionic liquid comprises 1-vinyl-3-butyl imidazole bis (trifluoromethane sulfonyl) imide salt, 1-vinyl-3-ethyl imidazole bis (trifluoromethane sulfonyl) imide salt, 1-allyl-3-ethyl imidazole bis (trifluoromethane sulfonyl) imide salt; 1-allyl-3-methylimidazolium hexafluorophosphate.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses environment-friendly organic solvent, has low ozone consumption potential and global warming potential;
2. the organic solvent used in the invention can be recycled, so that the production cost is reduced;
3. the ethylene-tetrafluoroethylene copolymer prepared by the invention has excellent mechanical properties, the tensile strength is more than or equal to 50MPa, and the elongation at break is more than or equal to 400%.
Drawings
FIG. 1 is a Fourier infrared spectrum of example 1;
FIG. 2 is a drawing showing a structure of example 1 19 F, NMR spectrum;
FIG. 3 is a DSC chart of example 1;
FIG. 4 is a TG curve of example 1.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
< example 1>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 5kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.02kg of liquid-phase monomer perfluorobutyl ethylene and 0.01kg of chain transfer agent methanol into a 10L stainless steel polymerization kettle, starting stirring, wherein the stirring speed is 60rpm, the temperature of the polymerization kettle is increased to 45 ℃, introducing a first mixed gas of ethylene and tetrafluoroethylene until the pressure of the polymerization kettle is 1200kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: 2, adding 0.006kg of tert-butyl peroxypivalate as an initiator to initiate copolymerization.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 0.5, maintaining the pressure of the polymerization kettle at 1200kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.45kg, discharging the polymerization kettle by pressure relief, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 2>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 5kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.02kg of liquid-phase monomer perfluorohexylethylene and 0.03kg of chain transfer agent n-hexane into a 10L stainless steel polymerization kettle, starting stirring, wherein the stirring speed is 60rpm, heating the polymerization kettle to 45 ℃, introducing a first mixed gas of ethylene and tetrafluoroethylene until the polymerization kettle pressure is 1200kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: 2, adding 0.006kg of tert-butyl peroxypivalate as an initiator to initiate copolymerization.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 0.5, maintaining the pressure of the polymerization kettle at 1200kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.45kg, discharging the polymerization kettle by pressure relief, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 3>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 5kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.04kg of liquid-phase monomer perfluorobutyl vinyl ether and 0.06kg of chain transfer agent cyclohexane into a 10L stainless steel polymerization kettle, starting stirring, wherein the stirring speed is 80rpm, heating the polymerization kettle to 55 ℃, introducing a first mixed gas of ethylene and tetrafluoroethylene until the polymerization kettle pressure is 1400kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: and 4, adding 0.01kg of tert-butyl peroxyisobutyrate as an initiator to initiate copolymerization reaction.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 1, maintaining the pressure of a polymerization kettle at 1400kPa, stopping copolymerization when the consumption of the second mixed monomer reaches 0.60kg, discharging the polymerization kettle by pressure relief, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 4>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 5kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.06kg of liquid-phase monomer perfluorobutyl vinyl ether and 0.06kg of chain transfer agent acetone into a 10L stainless steel polymerization kettle, starting stirring, wherein the stirring speed is 80rpm, heating the polymerization kettle to 65 ℃, introducing a first mixed gas of ethylene and tetrafluoroethylene until the polymerization kettle pressure is 1400kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: and 4, adding 0.01kg of tert-butyl peroxyisobutyrate as an initiator to initiate copolymerization reaction.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 1, maintaining the pressure of a polymerization kettle at 1400kPa, stopping copolymerization when the consumption of the second mixed monomer reaches 0.60kg, discharging the polymerization kettle by pressure relief, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 5>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: 6kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.12kg of liquid-phase monomer hexafluoropropylene, 0.06kg of chain transfer agent cyclohexane, 0.001kg of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 0.0001kg of vinyl ferrocene are added into a 10L stainless steel polymerization kettle, stirring is started, the stirring speed is 90rpm, the polymerization kettle is heated to 65 ℃, first mixed gas of ethylene and tetrafluoroethylene is introduced until the pressure of the polymerization kettle is 1400kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: and 6, adding 0.01kg of tert-butyl peroxyisobutyrate as an initiator to initiate copolymerization reaction.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 1.2, maintaining the pressure of the polymerization kettle at 1400kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.65kg, decompressing and discharging the polymerization kettle, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 6>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 6kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.16kg of liquid phase monomer hexafluoropropylene, 0.08kg of chain transfer agent cyclohexane, 0.004kg of 1-vinyl-3-ethylimidazole bistrifluoromethanesulfonylimide salt and 0.001kg of vinyl ferrocene into a 10L stainless steel polymerization kettle, starting stirring at the stirring speed of 100rpm, heating the polymerization kettle to 70 ℃, introducing a first mixed gas of ethylene and tetrafluoroethylene until the pressure of the polymerization kettle is 1450kPa, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: 6, 0.01kg of diisopropyl peroxydicarbonate as an initiator is added to initiate copolymerization.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 1.5, maintaining the pressure of the polymerization kettle at 1450kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.65kg, discharging the polymerization kettle by pressure relief, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 7>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: 6kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.12kg of liquid-phase monomer hexafluoroisobutylene, 0.08kg of chain transfer agent methanol, 0.008kg of 1-allyl-3-ethylimidazole bis (trifluoromethanesulfonyl) imide salt and 0.005kg of vinyl ferrocene are added into a 10L stainless steel polymerization kettle, stirring is started, the stirring speed is 110rpm, the polymerization kettle is heated to 80 ℃, a first mixed gas of ethylene and tetrafluoroethylene is introduced until the polymerization kettle pressure is 1550kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: 8, 0.01kg of diisopropyl peroxydicarbonate as an initiator is added to initiate the copolymerization reaction.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 1.8, maintaining the pressure of the polymerization kettle at 1550kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.75kg, decompressing and discharging the polymerization kettle, degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
< example 8>
A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: 6kg of organic solvent 2, 3-dichlorooctafluorobutane, 0.16kg of liquid-phase monomer hexafluoroisobutylene, 0.08kg of chain transfer agent acetone, 0.01kg of 1-allyl-3-methylimidazolium hexafluorophosphate and 0.01kg of vinyl ferrocene are added into a 10L stainless steel polymerization kettle, stirring is started, the stirring speed is 120rpm, the polymerization kettle is heated to 85 ℃, a first mixed gas of ethylene and tetrafluoroethylene is introduced into the polymerization kettle until the pressure of the polymerization kettle is 1600kPa, and the molar ratio of the ethylene to the tetrafluoroethylene in the first mixture is 1: 8, adding 0.01kg of initiator di-n-propyl peroxydicarbonate to initiate copolymerization.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, wherein the molar ratio of the ethylene to the tetrafluoroethylene in the second mixture is 1: 2.0, maintaining the pressure of the polymerization kettle at 1600kPa, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 0.75kg, discharging the pressure of the polymerization kettle in a pressure relief manner, and degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
EXAMPLES evaluation
Table 1 examples test items and standard methods
Table 2 example test results
Claims (10)
1. A method for preparing an ethylene-tetrafluoroethylene copolymer, comprising the steps of:
s1: adding 500-600 parts of organic solvent, 2-8 parts of liquid-phase monomer and 0.3-2.4 parts of chain transfer agent into a polymerization kettle according to parts by weight, starting stirring, wherein the stirring speed is 60-120rpm, heating the polymerization kettle to the reaction temperature, introducing first mixed gas of ethylene and tetrafluoroethylene to the pressure of the polymerization kettle to the reaction pressure, and adding 0.01-0.1 part of initiator to initiate copolymerization.
S2: and (3) after the polymerization reaction is started, introducing a second mixed gas of ethylene and tetrafluoroethylene, maintaining the pressure of the polymerization kettle, stopping the copolymerization reaction when the consumption of the second mixed monomer reaches 45-85 parts, decompressing and discharging the polymerization kettle, degassing and drying the obtained slurry to obtain the ethylene-tetrafluoroethylene copolymer resin.
2. The method of claim 1, wherein: the organic solvent is selected from 2, 3-dichlorooctafluorobutane, and the solvent can enter a solvent storage tank after being recovered and separated after the reaction is finished and can be recycled.
3. The method of claim 1, wherein: the liquid-phase monomer is selected from one or more mixtures of perfluoroalkyl ethylene, perfluoroalkyl vinyl ether, hexafluoropropylene and hexafluoroisobutylene.
4. The method of claim 1, wherein: the chain transfer agent is selected from one or more mixtures of alcohols, esters, ethers, ketones, alkanes and aromatics.
5. The method of claim 1, wherein: the initiator is selected from one or more mixtures of peroxyalcohol, peroxyacid, peroxyester, peroxyacyl, azo compound, persulfate, perchlorate, permanganate and the like.
6. The method of claim 1, wherein: the molar ratio of ethylene to tetrafluoroethylene in the first mixture is 1: 2-8, wherein the molar ratio of ethylene to tetrafluoroethylene in the second mixture is 1: 0.5 to 2.0.
7. The method of claim 1, wherein: the polymerization temperature is 45-85 ℃, and the polymerization pressure is 1200-1600 kPa.
8. The method of claim 1, wherein: 0.001-0.01 part of alkenyl ionic liquid and 0.0001-0.01 part of vinyl ferrocene can also be added into the S1 to participate in the reaction, wherein the alkenyl ionic liquid comprises vinyl and allyl ionic liquid.
9. The method of claim 8, wherein: the alkenyl ionic liquid cation comprises three main groups of 1-vinyl-3-alkyl imidazole, 1-allyl 3-vinyl imidazole and the like, wherein alkyl groups comprise methyl, ethyl, butyl and the like; the anions comprise chlorine, bromine, tetrafluoroboric acid, hexafluorophosphoric acid, bistrifluoromethanesulfonylimide and the like.
10. The method of claim 8, wherein: the alkenyl ionic liquid comprises 1-vinyl-3-butyl imidazole bis (trifluoromethane sulfonyl) imide salt, 1-vinyl-3-ethyl imidazole bis (trifluoromethane sulfonyl) imide salt and 1-allyl-3-ethyl imidazole bis (trifluoromethane sulfonyl) imide salt; 1-allyl-3-methylimidazolium hexafluorophosphate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115490799A (en) * | 2022-10-10 | 2022-12-20 | 浙江巨圣氟化学有限公司 | Preparation method of ETFE resin for solar backboard |
| CN115975098A (en) * | 2023-02-09 | 2023-04-18 | 浙江巨圣氟化学有限公司 | Preparation method of ethylene-tetrafluoroethylene copolymer for powder spraying |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243607A (en) * | 1990-02-20 | 1991-10-30 | Asahi Glass Co Ltd | Production of ethylene-tetrafluoroethylene copolymer |
| CN108440702A (en) * | 2018-03-19 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer |
| CN113501904A (en) * | 2021-07-30 | 2021-10-15 | 浙江巨圣氟化学有限公司 | Preparation method of perfluoroalkyl vinyl ether copolymer |
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2022
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03243607A (en) * | 1990-02-20 | 1991-10-30 | Asahi Glass Co Ltd | Production of ethylene-tetrafluoroethylene copolymer |
| CN108440702A (en) * | 2018-03-19 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of preparation method of high thermal stability ethylene-tetrafluoroethylene copolymer |
| CN113501904A (en) * | 2021-07-30 | 2021-10-15 | 浙江巨圣氟化学有限公司 | Preparation method of perfluoroalkyl vinyl ether copolymer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115490799A (en) * | 2022-10-10 | 2022-12-20 | 浙江巨圣氟化学有限公司 | Preparation method of ETFE resin for solar backboard |
| CN115975098A (en) * | 2023-02-09 | 2023-04-18 | 浙江巨圣氟化学有限公司 | Preparation method of ethylene-tetrafluoroethylene copolymer for powder spraying |
| CN115975098B (en) * | 2023-02-09 | 2024-01-30 | 浙江巨圣氟化学有限公司 | Preparation method of ethylene-tetrafluoroethylene copolymer for powder spraying |
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