CN118126230A - Ethylene-tetrafluoroethylene tetrapolymer and preparation method thereof - Google Patents
Ethylene-tetrafluoroethylene tetrapolymer and preparation method thereof Download PDFInfo
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- CN118126230A CN118126230A CN202410249458.4A CN202410249458A CN118126230A CN 118126230 A CN118126230 A CN 118126230A CN 202410249458 A CN202410249458 A CN 202410249458A CN 118126230 A CN118126230 A CN 118126230A
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- ethylene
- tetrafluoroethylene
- perfluoroalkyl
- tetrapolymer
- fluoroalkyl acrylate
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- -1 Ethylene-tetrafluoroethylene Chemical group 0.000 title claims abstract description 245
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 title claims abstract description 80
- 229920006029 tetra-polymer Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 156
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 96
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 230000001502 supplementing effect Effects 0.000 claims abstract description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011737 fluorine Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 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 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- COAUHYBSXMIJDK-UHFFFAOYSA-N 3,3-dichloro-1,1,1,2,2-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)Cl COAUHYBSXMIJDK-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 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 3
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 claims description 3
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 37
- 239000000047 product Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 19
- XJSRKJAHJGCPGC-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XJSRKJAHJGCPGC-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 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 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229960004624 perflexane Drugs 0.000 description 6
- 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 6
- 238000005406 washing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 2
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009864 tensile test Methods 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
- 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
-
- 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
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
- C08F220/24—Esters containing halogen containing perhaloalkyl radicals
Landscapes
- 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 relates to the technical field of fluorine-containing polymers, and discloses an ethylene-tetrafluoroethylene tetrapolymer and a preparation method thereof. The method for preparing the ethylene-tetrafluoroethylene tetrapolymer comprises the following steps: mixing an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator under the condition of vacuum and no water, adding tetrafluoroethylene, ethylene and an initiator into the obtained mixture for polymerization reaction, and continuously supplementing the tetrafluoroethylene, the ethylene, the perfluoroalkyl ethylene and the fluoroalkyl acrylate after the polymerization reaction starts. According to the method, the fluoroalkyl acrylate is added to control the polymer composition, so that the quadripolymer resin with controllable composition and uniform distribution is prepared, and the resin has low Young modulus, high flexibility and heat resistance on the premise of keeping good tensile strength.
Description
Technical Field
The invention relates to the technical field of fluorine-containing polymers, in particular to an ethylene-tetrafluoroethylene tetrapolymer and a preparation method thereof.
Background
Ethylene-tetrafluoroethylene copolymer (ETFE), also known as fluoroplastic-40, is a class of tetrafluoroethylene copolymers developed subsequent to FEP. ETFE is a semi-crystalline, translucent polymer formed by copolymerizing ethylene and tetrafluoroethylene. ETFE belongs to a tough material, and has good radiation resistance, chemical resistance and electrical insulation performance, and simultaneously has greatly improved radiation resistance and mechanical properties. However, with the wide spread of ETFE products, their higher young's modulus becomes a limiting factor for their application in certain fields, such as flexible films or cables.
Patent application CN102471414a discloses ETFE containing recurring units (a) based on TFE and recurring units (B) based on ethylene in molar ratio of recurring units (a)/recurring units (B) =66/34-75/25, containing 0-1 mol% of recurring units (C) based on a monomer represented by CH 2＝CX(CF2)n Y as an arbitrary component, relative to the total mole number of recurring units (a) based on tetrafluoroethylene and recurring units (B) based on ethylene, wherein X, Y is independently a hydrogen atom or a fluorine atom, and n is an integer of 2-8. Although the ETFE has good flexibility and heat resistance, the tensile strength of the ETFE is obviously reduced, and the application requirement cannot be met.
Therefore, there is a need to develop ETFE that also has high flexibility and high melting point while maintaining good tensile strength.
Disclosure of Invention
The invention aims to solve the problem that the ethylene-tetrafluoroethylene copolymer in the prior art cannot simultaneously maintain good tensile strength, high flexibility and high melting point, and provides an ethylene-tetrafluoroethylene tetrapolymer and a preparation method thereof.
To achieve the above object, a first aspect of the present invention provides a method for producing an ethylene-tetrafluoroethylene tetrapolymer, the method comprising: mixing an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator under the conditions of vacuum and no water, adding tetrafluoroethylene, ethylene and an initiator into the obtained mixture for polymerization reaction, and continuously supplementing tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate after the polymerization reaction starts; wherein the structural general formula of the perfluoroalkyl ethylene is CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8, and the fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, perfluoroalkyl methacrylate and perfluorosulfonamide methacrylate.
Preferably, the perfluoroalkyl ethylene is at least one of CH2＝CF(CF2)2F、CH2＝CF(CF2)4F、CH2＝CF(CF2)4H、CH2＝CH(CF2)4F、CH2＝CH(CF2)6F and CH 2＝CH(CF2)8 H.
Preferably, the fluoroalkyl acrylate is perfluoroalkyl methacrylate, and the structural general formula of the perfluoroalkyl methacrylate is Rf (CH 2)mOC(O)C(CH3)＝CH2, where Rf represents fluoroalkyl, and m is an integer from 0 to 4.
Preferably, the perfluoroalkyl ethylene added after the start of the polymerization reaction is 40-50wt% of the total amount of perfluoroalkyl ethylene, and the fluoroalkyl acrylate added after the start of the polymerization reaction is 20-50wt% of the total amount of fluoroalkyl acrylate.
Preferably, tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate are used in such an amount that the ethylene-tetrafluoroethylene tetrapolymer is produced with a content of repeating units provided by ethylene of 35 to 60 mol%, a content of repeating units provided by tetrafluoroethylene of 35 to 60 mol%, a content of repeating units provided by perfluoroalkyl ethylene of 0.5 to 10 mol%, and a content of repeating units provided by fluoroalkyl acrylate of 0.01 to 3 mol%.
Preferably, the tetrafluoroethylene and ethylene are used in amounts such that the ethylene-tetrafluoroethylene tetrapolymer is prepared with a molar ratio of repeating units provided by ethylene to repeating units provided by tetrafluoroethylene of 40/60 to 60/40.
Preferably, the perfluoroalkyl ethylene and fluoroalkyl acrylate are used in amounts such that the molar ratio of repeating units provided by the perfluoroalkyl ethylene to repeating units provided by the fluoroalkyl acrylate in the ethylene-tetrafluoroethylene tetrapolymer produced is 50/1 to 1/1.
Preferably, the organic solvent is at least one of a chlorofluorocarbon, a fluorinated hydrocarbon, a hydrofluoroether, a chlorinated hydrocarbon, an alcoholic organic solvent, and a hydrocarbon organic solvent.
Preferably, the molecular weight regulator is at least one of methanol, ethanol, acetone, pentane, hexane, cyclohexane and dichloropentafluoropropane.
Preferably, the initiator is at least one of tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate.
Preferably, the polymerization conditions include: the temperature is 10-100deg.C, the pressure is 0.1-5MPa, and the time is 1-10h.
In a second aspect, the invention provides an ethylene-tetrafluoroethylene tetrapolymer prepared by the method described above.
Preferably, the melt index of the ethylene-tetrafluoroethylene tetrapolymer ranges from 5 to 40g/10min.
Preferably, the parameters of the ethylene-tetrafluoroethylene tetrapolymer include: the melting point is 240-270 ℃, young's modulus is below 400MPa, tensile strength is above 40MPa, and elongation is above 300%.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) According to the ethylene-tetrafluoroethylene tetrapolymer, the composition of the polymer is controlled through the repeated units provided by fluoroalkyl acrylate on the basis of the original terpolymer, so that the tetrapolymer resin with controllable composition and uniform distribution is obtained;
(2) According to the preparation method of the ethylene-tetrafluoroethylene tetrapolymer, the ETFE resin with good tensile strength, lower Young modulus and higher melting point is obtained by regulating and controlling the process formula and the polymerization process;
(3) The ethylene-tetrafluoroethylene quadripolymer has flexibility and heat resistance, and can be applied to flexible films or cables.
Drawings
FIG. 1 is an infrared spectrum of an ethylene-tetrafluoroethylene tetrapolymer according to the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The preparation method of the ethylene-tetrafluoroethylene tetrapolymer comprises the following steps:
Mixing an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator under the condition of vacuum and no water, adding tetrafluoroethylene, ethylene and an initiator into the obtained mixture for polymerization reaction, and continuously supplementing the tetrafluoroethylene, the ethylene, the perfluoroalkyl ethylene and the fluoroalkyl acrylate after the polymerization reaction starts. According to the method disclosed by the invention, the polymer composition is controlled by adding the fluoroalkyl acrylate, so that the quadripolymer resin with controllable composition and uniform distribution is prepared, has the characteristics of good tensile strength, lower Young modulus and higher melting point, has flexibility and heat resistance, and can be applied to flexible films or cables.
The general structural formula of the perfluoroalkyl ethylene can be CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8, and the fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, fluorine-containing perfluoroalkyl methacrylate and perfluorosulfonamide methacrylate.
In the method of the present invention, the perfluoroalkyl ethylene may be at least one of CH2＝CF(CF2)2F、CH2＝CF(CF2)4F、CH2＝CF(CF2)4H、CH2＝CH(CF2)4F、CH2＝CH(CF2)6F and CH 2＝CH(CF2)8 H. In order that the ethylene-tetrafluoroethylene tetrapolymer has both monomer reactivity and comprehensive properties of a copolymerization product, n in a structural general formula CH 2＝CX(CF2)n Y of the perfluoroalkyl ethylene is preferably an integer of 2-4, and the perfluoroalkyl ethylene is more preferably CH 2＝CH(CF2)4 F.
In the method of the present invention, the fluoroalkyl acrylate may be perfluoroalkyl methacrylate having a general structural formula of Rf (CH 2)mOC(O)C(CH3)＝CH2, wherein Rf represents fluoroalkyl and m is an integer of 0 to 4), and the perfluoroalkyl methacrylate is preferably CF3(CH2)2OC(O)C(CH3)＝CH2、F(CF2)2(CH2)2OC(O)C(CH3)＝CH2、F(CF2)2OC(O)C(CH3)＝CH2 or F (at least one of CF 2)4OC(O)C(CH3)＝CH2, more preferably F (CF 2)2OC(O)C(CH3)＝CH2 (perfluoroalkyl methacrylate) in order to secure heat resistance and chemical stability of the ethylene-tetrafluoroethylene tetrapolymer.
In the method of the present invention, the organic solvent may be at least one of a chlorofluorocarbon, a fluorinated hydrocarbon, a hydrofluoroether, a chlorinated hydrocarbon, an alcoholic organic solvent, and a hydrocarbon organic solvent. The fluorochlorohydrocarbon may be, for example, trifluorotrichloroethane, the fluorinated hydrocarbon may be, for example, perfluorohexane, the hydrofluoroether may be, for example, tetrafluoroethyltrifluoroethyl ether, the chlorinated hydrocarbon may be, for example, pentachloroethane, the alcoholic organic solvent may be, for example, propanol, and the hydrocarbon organic solvent may be, for example, acetone. In order to ensure chain transfer effect, monomer solubility and environmental protection requirements of the organic solvent, the organic solvent is preferably a fluorinated hydrocarbon and/or a hydrofluoroether. The organic solvent is more preferably perfluorohexane, and the specific perfluorohexane may be 1H perfluorohexane.
In the method of the present invention, the molecular weight regulator may be at least one of methanol, ethanol, acetone, pentane, hexane, cyclohexane, and dichloropentafluoropropane. In order to ensure the mechanical properties and processability of the ethylene-tetrafluoroethylene tetrapolymer, the molecular weight regulator is preferably methanol.
In the process according to the invention, the initiator may be a free radical initiator, preferably an initiator having a half-life of 10 hours at a temperature of 10-100 ℃, and may specifically be, for example, at least one of t-butyl peroxypivalate, t-butyl peroxyisobutyrate, diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate, preferably t-butyl peroxypivalate.
In the method of the present invention, the polymerization conditions include: the temperature may be 10-100deg.C, preferably 60-80deg.C; the pressure may be 0.1-5MPa, preferably 1-3MPa; the time may be 1 to 10 hours, preferably 2 to 8 hours. Herein, the pressure is gauge pressure.
In the method of the invention, the vacuum and anhydrous conditions can remove oxygen from the polymerization kettle by vacuum. The vacuum may be applied by pumping a vacuum through nitrogen in the polymerization vessel. The polymerizer may be a vertical stainless steel polymerizer containing a stirring device. The stirring speed of the stirring device may be 500-700rpm, preferably 550-650rpm.
In the method of the present invention, the polymerization reaction process by adding tetrafluoroethylene, ethylene and an initiator to the obtained mixture comprises: the temperature of the polymerization kettle can be raised to 10-100 ℃, preferably 60-80 ℃; adding a mixed gas of the tetrafluoroethylene and the ethylene to the obtained mixture until the pressure is 0.1-5MPa, preferably 1-3MPa; the initiator is then added to the resulting mixture by means of an auxiliary pump.
In the method of the present invention, the molar ratio of the organic solvent, the perfluoroalkyl ethylene, the fluoroalkyl acrylate, and the molecular weight regulator may be (40-80): (0.5-1.5): (0.02-0.15): 1, preferably (45-78): (0.6-1): (0.05-0.12): 1. the molar ratio of the ethylene to the tetrafluoroethylene may be 1: (3-6), preferably 1: (4-5.5). The initiator and the molecular weight regulator may be (0.01-0.03): 1, preferably (0.013-0.023): 1.
In the method of the present invention, after the start of the polymerization reaction, the continuous addition of tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate comprises: after the polymerization reaction starts, continuing to supplement the mixed gas of the tetrafluoroethylene and the ethylene until the pressure is kept stable, and continuing to supplement the perfluoroalkyl ethylene and the fluoroalkyl acrylate by using a metering pump. To ensure the compositional stability of the ethylene-tetrafluoroethylene tetrapolymer, tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate are continuously fed to the end of the reaction after the polymerization reaction has begun to maintain the concentration of reactants.
In the process according to the invention, the perfluoroalkyl ethylene fed after the start of the polymerization reaction represents 40 to 50% by weight, preferably 42 to 45% by weight, of the total amount of perfluoroalkyl ethylene; the fluoroalkylacrylate to be added after the start of the polymerization reaction represents 20 to 50% by weight, preferably 25 to 50% by weight, based on the total amount of fluoroalkylacrylate.
In the method of the present invention, in continuing to add tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate, the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene may be 50 to 60 mol%, preferably 52 to 57 mol%; the content of the ethylene in the mixed gas of the tetrafluoroethylene and the ethylene may be 40 to 50 mol%, preferably 43 to 48 mol%; the molar ratio of perfluoroalkyl ethylene to fluoroalkyl acrylate may be (5-30): 1, preferably (6.5-12): 1.
In the process according to the invention, tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate are used in such amounts that the ethylene-tetrafluoroethylene tetrapolymer is produced with a content of repeating units provided by ethylene of from 35 to 60 mol%, preferably from 35 to 50 mol%; the content of the repeating unit provided by tetrafluoroethylene may be 35 to 60 mol%, preferably 50 to 60 mol%; the content of the repeating unit provided by the perfluoroalkyl ethylene may be 0.5 to 10 mol%, specifically, for example, may be 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol%, and in order to secure mechanical properties and heat resistance of the ethylene-tetrafluoroethylene tetrapolymer, it is preferably 1 to 7 mol%, more preferably 1.1 to 2.5 mol%; the content of the repeating unit provided by the fluoroalkyl acrylate may be 0.01 to 3 mol%, specifically, may be, for example, 0.01 mol%, 0.05 mol%, 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, or 3 mol%, and is preferably 0.05 to 1.5 mol%, more preferably 0.05 to 0.5 mol% in order to secure mechanical properties and heat resistance of the ethylene-tetrafluoroethylene tetrapolymer.
In the process according to the invention, the tetrafluoroethylene and ethylene are used in such amounts that the molar ratio of the repeating units provided by ethylene to the repeating units provided by tetrafluoroethylene in the ethylene-tetrafluoroethylene tetrapolymer prepared may be 40/60 to 60/40, in particular, for example, 40/60, 45/60, 50/50, 55/50, 60/50 or 60/40. In order to secure the mechanical properties and heat resistance of the ethylene-tetrafluoroethylene tetrapolymer, the molar ratio of the repeating units provided by ethylene to the repeating units provided by tetrafluoroethylene is preferably 40/60 to 50/50.
In the process according to the invention, the perfluoroalkyl ethylene and fluoroalkyl acrylate are used in such an amount that the molar ratio of the repeating units provided by the perfluoroalkyl ethylene to the repeating units provided by the fluoroalkyl acrylate in the ethylene-tetrafluoroethylene tetrapolymer prepared may be 50/1 to 1/1, in particular 45/1, 40/1, 35/1, 30/1, 25/1, 20/1, 15/1, 10/1, 5/1 or 1/1, for example. In order to ensure the mechanical properties and heat resistance of the ethylene-tetrafluoroethylene tetrapolymer, the molar ratio of the repeating units provided by the perfluoroalkyl ethylene to the repeating units provided by the fluoroalkyl acrylate is preferably 30/1 to 5/1, more preferably 20/1 to 5/1.
In the method according to the present invention, the method may further include: stopping the reaction, recovering the unreacted tetrafluoroethylene and the ethylene, and washing and drying the obtained product. The washing may be performed by an organic solvent to wash the product, and may be, for example, trifluorotrichloroethane, perfluorohexane, acetone or propanol, preferably perfluorohexane, and the specific perfluorohexane may be 1H perfluorohexane. The drying conditions include: the temperature may be 100-140 ℃, preferably 110-130 ℃; the time may be 6 to 10 hours, preferably 7 to 9 hours.
In some embodiments, the method of preparing an ethylene-tetrafluoroethylene tetrapolymer according to the present invention comprises the steps of:
(1) Vacuum dewatering and deoxidizing a polymerization kettle, adding an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator into the polymerization kettle, and mixing at a stirring speed of 500-700rpm, wherein the molar ratio of the organic solvent to the perfluoroalkyl ethylene to the fluoroalkyl acrylate to the molecular weight regulator is (40-80): (0.5-1.5): (0.02-0.15): 1, raising the temperature of the polymerization kettle to 10-100 ℃, and adding the ethylene and the tetrafluoroethylene into the obtained mixture in a molar ratio of 1: the mixed gas of the tetrafluoroethylene and the ethylene of (3-6) to a pressure of 0.1-5MPa; adding the initiator into the obtained mixture by an auxiliary pump to carry out polymerization reaction, wherein the initiator and the molecular weight regulator are (0.01-0.03): 1, a step of;
(2) Continuing to supplement the mixed gas of the tetrafluoroethylene and the ethylene until the pressure is kept stable after the polymerization reaction starts, wherein the content of the tetrafluoroethylene in the mixed gas of the tetrafluoroethylene and the ethylene is 50-60 mol%, and continuously supplementing the perfluoroalkyl ethylene (wherein the supplemented perfluoroalkyl ethylene accounts for 40-50wt% of the total amount of the perfluoroalkyl ethylene after the polymerization reaction starts) and the fluoroalkyl acrylate (wherein the supplemented fluoroalkyl acrylate accounts for 20-50wt% of the total amount of the fluoroalkyl acrylate after the polymerization reaction starts) with a metering pump, and the molar ratio of the perfluoroalkyl ethylene and the fluoroalkyl acrylate is (5-30): stopping the reaction after 1,1-10 hours, recovering unreacted tetrafluoroethylene and ethylene, and washing and drying the obtained product;
Wherein the structural general formula of the perfluoroalkyl ethylene is CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8, the fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, perfluoroalkyl methacrylate and perfluorosulfonamide methacrylate, the organic solvent is at least one of chlorofluorocarbon, fluorinated hydrocarbon, hydrofluoroether, chlorinated hydrocarbon, alcohol organic solvent and hydrocarbon organic solvent, the molecular weight regulator is at least one of methanol, ethanol, acetone, pentane, hexane, cyclohexane and dichloropentafluoropropane, and the initiator is a free radical initiator.
In other embodiments, the method of preparing an ethylene-tetrafluoroethylene tetrapolymer according to the present invention comprises the steps of:
(1) Vacuum dewatering and deoxidizing a polymerization kettle, adding an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator into the polymerization kettle, and mixing at a stirring speed of 550-650rpm, wherein the molar ratio of the organic solvent to the perfluoroalkyl ethylene to the fluoroalkyl acrylate to the molecular weight regulator is (45-78): (0.6-1): (0.05-0.12): 1, raising the temperature of a polymerization kettle to 60-80 ℃, and adding the ethylene and the tetrafluoroethylene into the obtained mixture in a molar ratio of 1: (4-5.5) said tetrafluoroethylene and said ethylene to a pressure of 1-3MPa; adding the initiator into the obtained mixture by an auxiliary pump to carry out polymerization reaction, wherein the initiator and the molecular weight regulator are (0.013-0.023): 1, a step of;
(2) Continuing to supplement the mixed gas of the tetrafluoroethylene and the ethylene until the pressure is kept stable after the polymerization reaction starts, wherein the content of the tetrafluoroethylene in the mixed gas of the tetrafluoroethylene and the ethylene is 52 to 57 mol%, and continuously supplementing the perfluoroalkyl ethylene (wherein the supplemented perfluoroalkyl ethylene accounts for 42 to 45wt% of the total amount of the perfluoroalkyl ethylene after the polymerization reaction starts) and the fluoroalkyl acrylate (wherein the supplemented fluoroalkyl acrylate accounts for 25 to 50wt% of the total amount of the fluoroalkyl acrylate after the polymerization reaction starts) with a metering pump, and the molar ratio of the perfluoroalkyl ethylene and the fluoroalkyl acrylate is (6.5 to 12): stopping the reaction after 1,2-8 hours, recovering unreacted tetrafluoroethylene and ethylene, and washing and drying the obtained product;
Wherein the structural general formula of the perfluoroalkyl ethylene is CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8, the fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, perfluoroalkyl methacrylate and perfluorosulfonamide methacrylate, the organic solvent is at least one of chlorofluorocarbon, fluorinated hydrocarbon, hydrofluoroether, chlorinated hydrocarbon, alcohol organic solvent and hydrocarbon organic solvent, the molecular weight regulator is at least one of methanol, ethanol, acetone, pentane, hexane, cyclohexane and dichloropentafluoropropane, and the initiator is a free radical initiator.
The invention also provides the ethylene-tetrafluoroethylene tetrapolymer prepared by the method, which contains an ethylene-based repeating unit, a tetrafluoroethylene-based repeating unit, a perfluoroalkyl ethylene-based repeating unit and a fluoroalkyl acrylate-based repeating unit, wherein the structural general formula of the perfluoroalkyl ethylene is CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8, and the fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, perfluoro nitrogen-containing fluoroalkyl methacrylate and perfluoro sulfonamide methacrylate. The ethylene-tetrafluoroethylene quadripolymer has the characteristics of controllable composition and uniform distribution, so that the ethylene-tetrafluoroethylene quadripolymer also has the characteristics of low Young's modulus, high flexibility and high melting point on the premise of keeping good tensile strength, and can be applied to flexible films or cables.
In the ethylene-tetrafluoroethylene tetrapolymer of the present invention, the perfluoroalkyl ethylene may be at least one of CH2＝CF(CF2)2F、CH2＝CF(CF2)4F、CH2＝CF(CF2)4H、CH2＝CH(CF2)4F、CH2＝CH(CF2)6F and CH 2＝CH(CF2)8 H. In order that the ethylene-tetrafluoroethylene tetrapolymer has both monomer reactivity and comprehensive properties of a copolymerization product, n in a structural general formula CH 2＝CX(CF2)n Y of the perfluoroalkyl ethylene is preferably an integer of 2-4, and the perfluoroalkyl ethylene is more preferably CH 2＝CH(CF2)4 F.
In the ethylene-tetrafluoroethylene tetrapolymer of the present invention, the fluoroalkyl acrylate may be perfluoroalkyl methacrylate having a general structural formula of Rf (CH 2)mOC(O)C(CH3)＝CH2, wherein Rf represents fluoroalkyl and m is an integer of 0 to 4), and in order to secure heat resistance and chemical stability of the ethylene-tetrafluoroethylene tetrapolymer, the perfluoroalkyl methacrylate is preferably at least one of CF3(CH2)2OC(O)C(CH3)＝CH2、F(CF2)2(CH2)2OC(O)C(CH3)＝CH2、F(CF2)2OC(O)C(CH3)＝CH2 and F (CF 2)4OC(O)C(CH3)＝CH2), more preferably F (CF 2)2OC(O)C(CH3)＝CH2 (perfluoroalkyl methacrylate).
In the ethylene-tetrafluoroethylene tetrapolymer of the present invention, the molecular weight of the ethylene-tetrafluoroethylene tetrapolymer may be represented by a melt index, and the melt index of the ethylene-tetrafluoroethylene tetrapolymer may range from 5 to 40g/10min, specifically, may be, for example, 5g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, 35g/10min or 40g/10min. In order to ensure mechanical properties and processability of the ethylene-tetrafluoroethylene tetrapolymer, the melt index of the ethylene-tetrafluoroethylene tetrapolymer is preferably in the range of 10 to 25g/10min. In the present invention, the melt index of the ethylene-tetrafluoroethylene tetrapolymer is subjected to a melt index test on a resin by a melt index meter, and the detection conditions may include: the temperature was 297℃and the load was 5kg.
In the ethylene-tetrafluoroethylene tetrapolymer of the present invention, the parameters of the ethylene-tetrafluoroethylene tetrapolymer may include: the melting point is 240-270 ℃, young's modulus is below 400MPa, tensile strength is above 40MPa, and elongation is above 300%. The ethylene-tetrafluoroethylene quadripolymer has obviously reduced Young modulus under the premise of keeping good tensile strength, has flexibility and heat resistance, and can be applied to flexible films or cables.
In some embodiments, the ethylene-tetrafluoroethylene tetrapolymer contains ethylene-based repeating units, tetrafluoroethylene-based repeating units, perfluoroalkyl ethylene-based repeating units, and fluoroalkyl acrylate-based repeating units, wherein the perfluoroalkyl ethylene has a structural formula of CH 2＝CX(CF2)n Y, wherein X and Y are each independently a hydrogen atom or a fluorine atom, n is an integer of 2 to 8, the fluoroalkyl acrylate is at least one of a perfluoroalkyl methacrylate, a sulfur-containing heteroatom perfluoroalkyl methacrylate, a perfluoro-nitrogen-containing fluoroalkyl methacrylate, and a perfluoro sulfonamide methacrylate, the ethylene-tetrafluoroethylene tetrapolymer has a repeating unit content of 35 to 60 mol%, a repeating unit content of 0.5 to 10 mol%, a repeating unit content of 0.01 to 3 mol%, a repeating unit content of 40 to 60 g/min of the tetrafluoroethylene copolymer, and a melt ratio of 40 to 60 g/min of 1 to 50 g/min of the tetrafluoroethylene copolymer is provided by melt ratio of 40 to 1 to 60 g/min of the perfluoroalkyl acrylate.
In other embodiments, the ethylene-tetrafluoroethylene tetrapolymer comprises ethylene-based repeat units, tetrafluoroethylene-based repeat units, perfluoroalkyl ethylene-based repeat units, and fluoroalkyl acrylate-based repeat units, wherein the perfluoroalkyl ethylene is at least one of CH2＝CF(CF2)2F、CH2＝CF(CF2)4F、CH2＝CF(CF2)4H、CH2＝CH(CF2)4F、CH2＝CH(CF2)6F and CH 2＝CH(CF2)8 H, the fluoroalkyl acrylate is a perfluoroalkyl methacrylate having the structural formula Rf (CH 2)mOC(O)C(CH3)＝CH2, wherein Rf represents a fluoroalkyl group, m is an integer from 0 to 4, the ethylene-tetrafluoroethylene tetrapolymer comprises ethylene-tetrafluoroethylene tetrapolymer having a repeat unit content of 35 to 50 mole percent, tetrafluoroethylene-based repeat unit content of 50 to 60 mole percent, perfluoroalkyl ethylene-based repeat unit content of 1.1 to 2.5 mole percent, perfluoroalkyl acrylate-based repeat unit content of 0.05 to 0.5 mole percent, ethylene-based repeat unit molar ratio of 40/60 to 60/60 to tetrafluoroethylene-based repeat unit content of 40.05 to 60.5 mole percent, and tetrafluoroethylene-based repeat unit content of 1 to 10 g/min melt index of the copolymer is 1 to 10 g/10 g.
The ethylene-tetrafluoroethylene tetrapolymer and the preparation method thereof according to the present invention are further described below by way of examples. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below are commercially available unless otherwise specified.
Example 1
Preparation of ethylene-tetrafluoroethylene tetrapolymer:
(1) A 5L vertical stainless steel polymerization kettle containing stirring equipment is vacuumized by filling nitrogen, 3300g of 1H perfluorohexane, 18g of perfluorobutyl ethylene, 3g of perfluoroalkyl ethyl methacrylate and 4g of methanol are mixed at a stirring speed of 600rpm, the temperature of the polymerization kettle is raised to 66 ℃, the mixture obtained is added with mixed gas of ethylene and tetrafluoroethylene (the mol percent is 20:80) to a pressure of 1.7MPa, and then 0.5g of tert-butyl peroxypivalate is added into the mixture obtained by an auxiliary pump for polymerization reaction;
(2) After the polymerization was started, the mixed gas of tetrafluoroethylene and ethylene (in which the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene was 52 mol%) was continuously fed, the polymerization pressure was kept stable, and the perfluoroalkyl ethylene and fluoroalkyl acrylate were continuously fed with a metering pump, when the amount of fed mixed gas of tetrafluoroethylene and ethylene reached 500g, the amount of fed perfluorobutyl ethylene was 14g, the reaction was stopped after 5 hours, the unreacted ethylene and tetrafluoroethylene were recovered by cooling, and the obtained product was washed with 1H perfluorohexane and dried at 120℃for 8 hours to obtain 437g of a resin product.
Example 2
Preparation of ethylene-tetrafluoroethylene tetrapolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, 22g of perfluorobutyl ethylene, 3.3g of perfluoroalkyl ethyl methacrylate and 5g of methanol, mixing at a stirring speed of 550rpm, heating the polymerization kettle to 60 ℃, adding a mixed gas (mol percent is 15:85) of ethylene and tetrafluoroethylene into the obtained mixture to a pressure of 1MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization was started, the mixed gas of tetrafluoroethylene and ethylene (in which the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene was 57 mol%) was continuously fed, the polymerization pressure was kept stable, and the perfluoroalkyl ethylene and fluoroalkyl acrylate were continuously fed with a metering pump, when the amount of the fed mixed gas of tetrafluoroethylene and ethylene reached 455g, the amount of the fed perfluorobutyl ethylene was 17g, the reaction was stopped after 1.2g, and after 1H, unreacted ethylene and tetrafluoroethylene were recovered by cooling, discharged through a discharge valve of the reaction vessel, and the obtained product was washed with 1H perfluorohexane, and dried at 100℃for 6H to obtain 417g of a resin product.
Example 3
Preparation of ethylene-tetrafluoroethylene tetrapolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, 40g of perfluorobutyl ethylene, 2g of perfluoroalkyl ethyl methacrylate and 7g of methanol, mixing at a stirring speed of 650rpm, heating the polymerization kettle to 80 ℃, adding a mixed gas (mol percent is 20:80) of ethylene and tetrafluoroethylene into the obtained mixture to a pressure of 1.7MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization was started, the mixed gas of tetrafluoroethylene and ethylene (in which the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene was 56 mol%) was continuously fed, the polymerization pressure was kept stable, and the perfluoroalkyl ethylene and fluoroalkyl acrylate were continuously fed with a metering pump, when the amount of fed tetrafluoroethylene and ethylene mixed gas reached 497g, the amount of fed perfluorobutyl ethylene was 30g, the reaction was stopped after 10 hours, unreacted ethylene and tetrafluoroethylene were recovered by cooling, and the obtained product was washed with 1H perfluorohexane and dried at 140 ℃ for 12 hours to obtain 480g of resin product.
Example 4
Preparation of ethylene-tetrafluoroethylene tetrapolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, 39g of perfluorobutyl ethylene, 4g of perfluoroalkyl ethyl methacrylate and 5g of methanol, mixing at a stirring speed of 600rpm, heating the polymerization kettle to 66 ℃, adding mixed gas (mol percent is 20:80) of ethylene and tetrafluoroethylene into the obtained mixture to a pressure of 1.7MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization was started, the mixed gas of tetrafluoroethylene and ethylene (in which the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene was 56 mol%) was continuously fed, the polymerization pressure was kept stable, and the perfluoroalkyl ethylene and fluoroalkyl acrylate were continuously fed with a metering pump, when the amount of the fed mixed gas of tetrafluoroethylene and ethylene reached 472g, the amount of the fed perfluorobutyl ethylene was 27g, the amount of the perfluoroalkyl ethyl methacrylate was 2.3g, the reaction was stopped after 5 hours, unreacted ethylene and tetrafluoroethylene were recovered by cooling, discharged through a discharge valve of the reaction vessel, and the obtained product was washed with 1H perfluorohexane, and dried at 140 ℃ for 12 hours to obtain 479g of a resin product.
Comparative example 1
Preparation of ethylene-tetrafluoroethylene binary copolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, mixing 4g of methanol at a stirring rotation speed of 600rpm, heating the polymerization kettle to 66 ℃, adding mixed gas (mol percent is 20:80) of ethylene and tetrafluoroethylene into the obtained mixture until the pressure is 1.7MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization was started, the mixed gas of tetrafluoroethylene and ethylene (the content of tetrafluoroethylene in the mixed gas of tetrafluoroethylene and ethylene was 56 mol%) was continuously fed, the polymerization pressure was kept stable, and when the fed mixed gas of tetrafluoroethylene and ethylene reached 400g, the reaction was stopped, unreacted ethylene and tetrafluoroethylene were recovered by cooling, discharged through a discharge valve of the reaction vessel, and the obtained product was washed with 1H perfluorohexane and dried at 120℃for 8 hours to obtain 410g of a resin product.
Comparative example 2
Preparation of ethylene-tetrafluoroethylene terpolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, 40g of perfluorobutyl ethylene and 5g of methanol, mixing at a stirring speed of 600rpm, heating the polymerization kettle to 66 ℃, adding mixed gas (mol percent is 20:80) of ethylene and tetrafluoroethylene into the obtained mixture to a pressure of 1.7MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization reaction starts, continuously adding mixed gas of tetrafluoroethylene and ethylene (wherein the content of the tetrafluoroethylene in the mixed gas of the tetrafluoroethylene and the ethylene is 56 mol percent), keeping the polymerization pressure stable, continuously adding the perfluoroalkyl ethylene by a metering pump, stopping the reaction after the added mixed gas of the tetrafluoroethylene and the ethylene reaches 449g and 5H, cooling to recover unreacted ethylene and the tetrafluoroethylene, discharging the unreacted ethylene and the tetrafluoroethylene through a discharge valve of a reaction kettle, washing the obtained product by 1H perfluorohexane, and drying at 120 ℃ for 8H to obtain 447g of resin product.
Comparative example 3
Preparation of ethylene-tetrafluoroethylene terpolymer:
(1) Charging nitrogen into a 5L vertical stainless steel polymerization kettle containing stirring equipment, vacuumizing, adding 3300g of 1H perfluorohexane, 50g of perfluorobutyl ethylene and 5g of methanol, mixing at a stirring speed of 600rpm, heating the polymerization kettle to 66 ℃, adding mixed gas (mol percent is 20:80) of ethylene and tetrafluoroethylene into the obtained mixture to a pressure of 1.7MPa, and adding 0.5g of tert-butyl peroxypivalate into the obtained mixture by an auxiliary pump for polymerization reaction;
(2) After the polymerization reaction starts, continuously adding mixed gas of tetrafluoroethylene and ethylene (wherein the content of the tetrafluoroethylene in the mixed gas of the tetrafluoroethylene and the ethylene is 56 mol percent), keeping the polymerization pressure stable, continuously adding the perfluoroalkyl ethylene by using a metering pump, stopping the reaction after the added mixed gas of the tetrafluoroethylene and the ethylene reaches to 480g, cooling to recover unreacted ethylene and the tetrafluoroethylene, discharging by using a discharge valve of a reaction kettle, washing the obtained product by using 1H perfluorohexane, and drying at 120 ℃ for 8H to obtain 447g of resin product.
Test example: the following tests were carried out on the resin products obtained in examples 1 to 4 and comparative examples 1 to 3:
(1) Preparing a tensile test spline by adopting a compression molding technology; tensile property tests were carried out according to GB/T1040.1-2006;
(2) And (3) carrying out melt index test on the resin by adopting a melt index instrument, wherein the test conditions are as follows: a temperature of 297 ℃,5kg load;
(3) Melting point test is carried out on the resin by adopting a Differential Scanning Calorimeter (DSC), and the temperature of the sample is raised to 300 ℃ from room temperature at the speed of 10 ℃/min;
(4) The intensity ratio of the specified groups was determined by infrared spectroscopy to obtain the composition of the copolymer, wherein A is a repeating unit provided by tetrafluoroethylene, B is a repeating unit provided by perfluoroalkyl ethylene, and C is a repeating unit provided by fluoroalkyl acrylate.
The composition, melting point, melt index, tensile strength, elongation and Young's modulus of the copolymer are recorded in Table 1.
TABLE 1
As can be seen from the results of Table 1, the examples using the ethylene-tetrafluoroethylene tetrapolymer of the present invention also have the characteristics of low Young's modulus, high flexibility and high melting point while maintaining good tensile strength. While the ethylene-tetrafluoroethylene copolymer has a lower tensile strength and a higher young's modulus, the ethylene-tetrafluoroethylene terpolymer cannot maintain both good tensile strength and a lower young's modulus.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A method of producing an ethylene-tetrafluoroethylene tetrapolymer, the method comprising:
Mixing an organic solvent, perfluoroalkyl ethylene, fluoroalkyl acrylate and a molecular weight regulator under the conditions of vacuum and no water, adding tetrafluoroethylene, ethylene and an initiator into the obtained mixture for polymerization reaction, and continuously supplementing tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate after the polymerization reaction starts;
Wherein the structural general formula of the perfluoroalkyl ethylene is CH 2＝CX(CF2)n Y, wherein X and Y are respectively and independently hydrogen atoms or fluorine atoms, n is an integer of 2-8,
The fluoroalkyl acrylate is at least one of perfluoroalkyl methacrylate, sulfur-containing heteroatom perfluoroalkyl methacrylate, fluorine-containing fluoroalkyl methacrylate and perfluoro sulfonamide methacrylate.
2. The method according to claim 1, wherein the perfluoroalkyl ethylene is at least one of CH2＝CF(CF2)2F、CH2＝CF(CF2)4F、CH2＝CF(CF2)4H、CH2＝CH(CF2)4F、CH2＝CH(CF2)6F and CH 2＝CH(CF2)8 H.
3. The method according to claim 1, wherein the fluoroalkyl acrylate is a perfluoroalkyl methacrylate having a general structural formula of Rf (CH 2)mOC(O)C(CH3)＝CH2, wherein Rf represents a fluoroalkyl group and m is an integer of 0 to 4.
4. A process according to any one of claims 1 to 3, characterized in that the total amount of perfluoroalkyl ethylene added after the start of the polymerization is 40-50 wt.% and the total amount of fluoroalkyl acrylate added after the start of the polymerization is 20-50 wt.%.
5. The method according to any one of claims 1 to 4, wherein tetrafluoroethylene, ethylene, perfluoroalkyl ethylene and fluoroalkyl acrylate are used in such an amount that the ethylene-tetrafluoroethylene tetrapolymer is produced with a content of repeating units provided by ethylene of 35 to 60 mol%, a content of repeating units provided by tetrafluoroethylene of 35 to 60 mol%, a content of repeating units provided by perfluoroalkyl ethylene of 0.5 to 10 mol%, and a content of repeating units provided by fluoroalkyl acrylate of 0.01 to 3 mol%.
6. The method of claim 5, wherein the tetrafluoroethylene and ethylene are used in amounts such that the ethylene-tetrafluoroethylene tetrapolymer is produced with a molar ratio of repeat units provided by ethylene to repeat units provided by tetrafluoroethylene of 40/60 to 60/40.
7. The method according to claim 5 or 6, wherein the amount of perfluoroalkyl ethylene and fluoroalkyl acrylate is such that the molar ratio of repeating units provided by perfluoroalkyl ethylene to repeating units provided by fluoroalkyl acrylate in the ethylene-tetrafluoroethylene tetrapolymer prepared is 50/1 to 1/1.
8. The method of claim 1, wherein the organic solvent is at least one of a chlorofluorocarbon, a fluorinated hydrocarbon, a hydrofluoroether, a chlorinated hydrocarbon, an alcoholic organic solvent, and a hydrocarbon organic solvent;
preferably, the molecular weight regulator is at least one of methanol, ethanol, acetone, pentane, hexane, cyclohexane and dichloropentafluoropropane;
Preferably, the initiator is at least one of tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, diisopropyl peroxydicarbonate and di-n-propyl peroxydicarbonate.
9. The method of claim 1, wherein the polymerization conditions comprise: the temperature is 10-100deg.C, the pressure is 0.1-5MPa, and the time is 1-10h.
10. An ethylene-tetrafluoroethylene tetrapolymer prepared by the process of any one of claims 1-9;
Preferably, the melt index of the ethylene-tetrafluoroethylene tetrapolymer ranges from 5 to 40g/10min;
Preferably, the parameters of the ethylene-tetrafluoroethylene tetrapolymer include: the melting point is 240-270 ℃, young's modulus is below 400MPa, tensile strength is above 40MPa, and elongation is above 300%.
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