CN108047189A - A kind of own cycloolefin of fluorine-containing dioxa, its homopolymer and preparation method thereof - Google Patents
A kind of own cycloolefin of fluorine-containing dioxa, its homopolymer and preparation method thereof Download PDFInfo
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- CN108047189A CN108047189A CN201711307870.3A CN201711307870A CN108047189A CN 108047189 A CN108047189 A CN 108047189A CN 201711307870 A CN201711307870 A CN 201711307870A CN 108047189 A CN108047189 A CN 108047189A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 52
- 239000011737 fluorine Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 15
- 229920001519 homopolymer Polymers 0.000 title description 4
- 150000001925 cycloalkenes Chemical class 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 7
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 21
- -1 carboxylic acid alkali metal salt Chemical class 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 claims description 11
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- PPVPVKZXQJZBRA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorobenzoyl) 2,3,4,5,6-pentafluorobenzenecarboperoxoate Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)OOC(=O)C1=C(F)C(F)=C(F)C(F)=C1F PPVPVKZXQJZBRA-UHFFFAOYSA-N 0.000 claims description 4
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003682 fluorination reaction Methods 0.000 claims description 4
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- CJFUEPJVIFJOOU-UHFFFAOYSA-N 2-perfluorobutyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1CCCO1 CJFUEPJVIFJOOU-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229960004624 perflexane Drugs 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- AJTMETZNJZUOHU-UHFFFAOYSA-M potassium;carbonofluoridate Chemical compound [K+].[O-]C(F)=O AJTMETZNJZUOHU-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 3
- 229920005548 perfluoropolymer Polymers 0.000 description 3
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JSGITCLSCUKHFW-UHFFFAOYSA-N 2,2,4-trifluoro-5-(trifluoromethoxy)-1,3-dioxole Chemical compound FC1=C(OC(F)(F)F)OC(F)(F)O1 JSGITCLSCUKHFW-UHFFFAOYSA-N 0.000 description 1
- SYKSRBWOTOSLBT-UHFFFAOYSA-N 4,6-dimethyl-2-methylidene-1,3-dioxane Chemical compound CC1CC(C)OC(=C)O1 SYKSRBWOTOSLBT-UHFFFAOYSA-N 0.000 description 1
- QBCCGEPNFFWJOU-UHFFFAOYSA-N 5H-furo[3,2-g]chromen-5-one Chemical compound C1=C2C(=O)C=COC2=CC2=C1C=CO2 QBCCGEPNFFWJOU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VLHOVNZJTJUSQU-UHFFFAOYSA-M sodium;carbonofluoridate Chemical compound [Na+].[O-]C(F)=O VLHOVNZJTJUSQU-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/18—Monomers containing fluorine
- C08F114/185—Monomers containing fluorine not covered by the groups C08F114/20 - C08F114/28
-
- 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
- C08F116/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a kind of fluorine-containing cyclic monomer of formula (I) structure and its fluoropolymer of formula (II) structure, which is the amorphous fluoropolymer prepared by homopolymerization.Six-membered ring structure in the polymer molecular chain destroys molecule regularity, and entire molecule is caused to be difficult to crystallize and amorphous state is presented.Amorphous fluoropolymer translucency that the present invention is prepared is good, mechanical property and excellent heat stability, there is good dissolubility in fluoride solvent, prepared thin polymer film mechanical strength and ductility are excellent, can be widely applied to optical coating, electronic device and seperation film field；
Description
Technical Field
The invention relates to the field of soluble amorphous fluorine-containing polymers, in particular to a fluorine-containing monomer, a fluorine-containing polymer and a preparation method thereof.
Background
Besides the advantages of high temperature resistance, chemical corrosion resistance, ultraviolet resistance and the like of the traditional fluororesin, the bulk material of the amorphous fluorine-containing polymer also has excellent solubility, high light transmission and low dielectric constant, so that the amorphous perfluoropolymer is easy to process and can be widely applied to the fields of electronics, chemical engineering, aerospace and the like as an optical coating, an optical fiber substrate and a gas and liquid separation membrane material.
The currently internationally commercially available brand of transparent amorphous fluoropolymers is available from DuPont, Inc. of SimuAF, Asahi glass company of JapanAnd of Solvay BelgiumAnd (3) AD. Wherein,AF andAD is prepared by copolymerizing perfluoro (2, 2-dimethyl-1, 3-dioxole) (PDD) and 5-trifluoromethoxy-2, 2, 4-trifluoro-1, 3-dioxole (TTD) with tetrafluoroethylene,the resin is a homopolymer obtained by performing cyclic radical polymerization on perfluoro (butene-3-yl vinyl ether) (PBVE), and a molecular chain comprises five-membered rings and six-membered rings and mainly comprises the five-membered rings. The preparation of the amorphous perfluoropolymer is mainly to introduce or construct a ring structure with large steric hindrance in a molecular chain so as to destroy the symmetry of the molecular chain, so that a crystalline state is difficult to form, and the polymer has an amorphous structure. However, the polymer prepared by the above method has a complicated preparation method and poor thermal stability.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a fluoropolymer, which has a simple preparation method and good thermal stability.
The invention provides a fluorine-containing monomer with a structure shown in a formula (I):
the invention provides a fluorine-containing polymer with a structure of a formula (II):
wherein n is the number of repeating units and is an integer greater than or equal to zero.
The invention provides a preparation method of a fluorine-containing monomer with a structure shown in a formula (I), which comprises the following steps:
a) reacting methyl pyruvate with 2, 4-pentanediol to obtain 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxycyclohexane;
b) 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane is fluorinated and neutralized to obtain fluorine-containing carboxylic acid alkali metal salt;
c) decomposing the fluorine-containing carboxylic acid alkali metal salt to obtain the monomer with the structure of the formula (I).
Preferably, the molar ratio of the methyl pyruvate and the 2, 4-pentanediol in the step a) is 1: 1; the solvent is selected from one or more of benzene and toluene; the catalyst is one or more selected from p-toluenesulfonic acid and Amberlyst-15 acid resin.
Preferably, the fluorination in the step b) is specifically performed by introducing fluorine gas with the concentration of 10-30% and fluorinating for 6-24 hours at the temperature of 0-20 ℃.
Preferably, the fluorinated solvent in step b) is one or more selected from perfluorohexane, perfluorobutyltetrahydrofuran and 1,1, 2-trichloro-trifluoroethane; the neutralization is performed by adding potassium hydroxide or sodium hydroxide.
Preferably, the decomposition in step c) is specifically: heating to 200-250 deg.C for decomposition.
The invention provides a preparation method of a fluorine-containing polymer with a structure of a formula (II), which comprises the following steps:
the monomer with the structure of the formula (I) is polymerized under the action of an initiator to obtain the polymer with the structure of the formula (II).
Preferably, the initiator is selected from one or more of perfluorobenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and perfluorodibutyryl peroxide.
Preferably, the polymerization is specifically: polymerizing for 1-8 hours at 30-65 ℃ under the condition of inert gas.
Compared with the prior art, the invention provides the fluorine-containing polymer with the structure shown in the formula (II), which is an amorphous fluorine-containing polymer prepared by homopolymerizing specific monomers. The six-membered ring structure in the molecular chain of the polymer destroys the molecular regularity, so that the whole molecule is difficult to crystallize and presents an amorphous state. The amorphous fluorine-containing polymer prepared by the method has good light transmission, excellent mechanical property and thermal stability, good solubility in fluorine-containing solvent, excellent mechanical strength and ductility of the prepared polymer film, and can be widely applied to the fields of optical coatings, electronic devices and separation membranes.
Detailed Description
The invention provides a fluorine-containing monomer, a fluorine-containing polymer and a preparation method thereof, and a person skilled in the art can realize the preparation by properly improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a fluorine-containing monomer with a structure shown in a formula (I):
the invention provides a preparation method of a fluorine-containing monomer with a structure shown in a formula (I), which comprises the following steps:
a) reacting methyl pyruvate with 2, 4-pentanediol to obtain 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxycyclohexane;
b) 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane is fluorinated and neutralized to obtain fluorine-containing carboxylic acid alkali metal salt;
c) decomposing the fluorine-containing carboxylic acid alkali metal salt to obtain the monomer with the structure of the formula (I).
The preparation method of the fluorine-containing monomer provided by the invention comprises the step of reacting methyl pyruvate with 2, 4-pentanediol to obtain 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane.
Specifically, methyl pyruvate and 2, 4-pentanediol are mixed according to a stoichiometric molar ratio of 1:1, placing the mixture in a reaction flask, adding a solvent and a catalyst, refluxing for 24-48 hours, and distilling out precursor 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane.
Wherein, the solvent is preferably selected from one or more of benzene and toluene; the catalyst is preferably selected from one or more of p-toluenesulfonic acid and Amberlyst-15 acidic resin.
2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane is fluorinated and neutralized to obtain fluorine-containing carboxylic acid alkali metal salt.
Wherein, the fluorination is preferably performed by introducing fluorine gas with the concentration of 10-30% and fluorinating for 6-24 hours at the temperature of 0-20 ℃; more preferably, fluorine gas with the concentration of 12-28% is introduced, and the mixture is fluorinated for 8-20 hours at the temperature of 2-18 ℃;
namely the steps are as follows: the obtained precursor 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane is dissolved in a solvent and is fluorinated. And neutralizing the product to be neutral after the reaction is finished to obtain the perfluorinated alkali metal salt. The fluorinated solvent is preferably selected from one or more of perfluorohexane, perfluorobutyltetrahydrofuran and 1,1, 2-trichloro-trifluoroethane; the neutralization is performed by adding potassium hydroxide or sodium hydroxide.
Decomposing the fluorine-containing carboxylic acid alkali metal salt to obtain the monomer with the structure of the formula (I).
Decomposing the perfluorinated alkali metal salt obtained in the step under the protection of nitrogen, and collecting the decomposition product in a dry ice-acetone bath to obtain a colorless transparent liquid product, wherein the liquid is a perfluorinated (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer.
Wherein the decomposition is specifically: heating to 200-250 deg.C for decomposition.
Wherein, the reaction route is as follows:
the invention obtains the monomer by ring closing, fluorination, purification and decarboxylation from the full-hydrocarbon raw material. The method has short operation steps, and high final yield and purity of the product.
Wherein n is the number of repeating units and is an integer greater than or equal to zero; the n is preferably an integer of 100 or more.
The invention provides a preparation method of a fluorine-containing polymer with a structure of a formula (II), which comprises the following steps:
the monomer with the structure of the formula (I) is polymerized under the action of an initiator to obtain the polymer with the structure of the formula (II).
The polymerization method of the perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) homopolymer can adopt bulk polymerization; well-known methods such as solution polymerization, suspension polymerization, emulsion polymerization, etc. may also be employed, and will not be described herein. When solution polymerization is employed, at least one of a fluorine-containing solvent FC-72 (3M), FC-75 (3M), and 1,1, 2-trifluoro-trichloroethane (CFC-113) may be used as the reaction solvent.
And performing bulk polymerization on the perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) (PMDD) obtained in the step. Specifically, an initiator is added into a monomer with a structure shown in formula (I), the reaction system is filled with inert gas after air is removed, polymerization reaction is carried out, and after the polymerization reaction is finished, unreacted monomers are distilled out to obtain a white high molecular product.
Specifically, the initiator is preferably selected from one or more of perfluorobenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and perfluorodibutyryl peroxide.
The polymerization is preferably specifically: polymerizing for 1-8 hours at 30-65 ℃ under the condition of inert gas; more preferably specifically: polymerizing for 4-8 hours at 40-65 ℃ under the condition of inert gas; the inert gas is preferably one of helium, nitrogen and argon; more preferably nitrogen.
The fluorine-containing polymer has high transparency and good solubility in fluorine-containing solvents, mainly because the six-membered ring structure in the molecular chain of the polymer destroys the molecular regularity, resulting in difficulty in crystallizing the whole molecule to assume an amorphous state. The polymer has excellent mechanical property and thermal stability, and is mainly benefited by the fact that the fluorine-containing dioxa-hexane cycloolefin monomer has higher reaction activity and high molecular weight.
The fluorine-containing polymer provided by the invention is transparent optical resin, is dissolved in a specific fluorine-containing solvent, and can form a coating or a film with corrosion resistance, low reflectivity and heat resistance by casting, coating and other modes. Can be applied to the fields of coating, film material, optical fiber, medical apparatus and the like.
The invention also provides a coating which is prepared by dissolving the fluorine-containing polymer in the fluorine-containing solvent.
The invention relates to a novel amorphous fluorine-containing polymer obtained by homopolymerization of perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer (PMDD). The fluorine-containing polymer meets all the excellent performances of the products, such as low dielectric constant, high thermal stability, low water absorption, low thermal expansion coefficient and the like, and the thermal stability is superior to that of Cytop. Different from the traditional Teflon material, the macromolecule can be dissolved in a fluorine-containing organic solvent, so that the solution coating and the perfect uniform coating manufacture are possible, and the method is particularly suitable for special coatings in the electronic manufacturing industry and coatings of devices with special shapes. It has perfect chemical stability, and has no chemical degradation after being soaked in hot concentrated sulfuric acid or concentrated sodium hydroxide solution for one month. Currently, there are only three companies that can produce amorphous perfluoropolymers in the world, namely DuPont, Suwei in Belgium and Asahi glass in Japan. The application development of the soluble fluorine-containing material is far from the mature degree.
In order to further illustrate the present invention, the following will describe in detail the fluoromonomer, the fluoropolymer and the method for producing the same provided by the present invention with reference to examples.
Example 1
102g of methyl pyruvate (1mol) and 104g of 2, 4-pentanediol (1mol) were mixed and placed in a 500mL three-necked flask, 150mL of toluene and 5g of p-toluenesulfonic acid were added, the water and the solvent in the system were distilled off through a water separator under reflux for 24 hours, and 35g of the fluorinated precursor, 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane, was obtained by distillation under reduced pressure. 5g of the obtained precursor was mixed in 200ml of FC-75, and the mixture was reacted at 20 ℃ for 24 hours by introducing 10% fluorine gas, followed by GC-MS. And after the reaction is finished, adding 5M sodium hydroxide aqueous solution into the reaction solution until the pH value is neutral, separating out a water phase, concentrating, and freeze-drying to obtain the sodium perfluorocarboxylate. Heating the obtained sodium salt of the perfluorocarboxylic acid to 200 ℃ in a nitrogen atmosphere to carry out thermal decomposition reaction, cooling a fraction receiving bottle by using a dry ice-acetone bath in the thermal decomposition process, and collecting colorless transparent liquid which is perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer.
Example 2
1020g methyl pyruvate (10mol), 1040g 2, 4-pentanediol (10mol) were mixed and placed in a 5L three-necked flask, 1000ml toluene and 20g amberlyst-15 dry resin were added. Refluxing for 48 hours, the water and solvent in the system were distilled off by a water separator, the catalyst resin was removed by filtration, and 485g of the fluorinated precursor, 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane, was obtained by distillation under reduced pressure of the mixed solution. 20g of the precursor thus obtained was mixed with 500ml of CFC-113, and the mixture was reacted at 0 ℃ for 10 hours by supplying fluorine gas at a concentration of 20% and followed by GC-MS. And after the reaction is finished, adding a 5M potassium hydroxide aqueous solution into the reaction solution until the pH value is neutral, separating out a water phase, concentrating, and freeze-drying to obtain the potassium perfluorocarboxylate. Heating the obtained potassium perfluorocarboxylate to 250 ℃ in a nitrogen atmosphere for thermal decomposition reaction, cooling a fraction receiving bottle by using a dry ice-acetone bath in the thermal decomposition process, and collecting colorless transparent liquid which is a perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer.
Example 3
102g of methyl pyruvate (1mol) and 104g of 2, 4-pentanediol (1mol) were mixed and placed in a 500mL three-necked flask, and 150mL of toluene and 2g of amberlyst-15 dry resin were added. After refluxing for 24 hours, the water and solvent in the system were distilled off by a water separator, the catalyst resin was removed by filtration, and the mixed solution was distilled under reduced pressure to obtain 45g of a fluorinated precursor, 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane. 10 g of the obtained precursor was mixed in 400ml of FC-75, and a 30% concentration fluorine gas was introduced to the mixture to carry out a reaction at 10 ℃ for 6 hours, followed by GC-MS. And after the reaction is finished, adding a 5M potassium hydroxide aqueous solution into the reaction solution until the pH value is neutral, separating out a water phase, concentrating, and freeze-drying to obtain the potassium perfluorocarboxylate. Heating the obtained potassium perfluorocarboxylate to 250 ℃ in a nitrogen atmosphere for thermal decomposition reaction, cooling a fraction receiving bottle by using a dry ice-acetone bath in the thermal decomposition process, and collecting colorless transparent liquid which is a perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer.
Example 4
102g of methyl pyruvate (1mol) and 104g of 2, 4-pentanediol (1mol) were mixed and placed in a 500mL three-necked flask, and 150mL of benzene and 5g of amberlyst-15 dry resin were added. After refluxing for 24 hours, the water and solvent in the system were distilled off by a water separator, the catalyst resin was removed by filtration, and 40g of the fluorinated precursor 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane was obtained by distilling the mixed solution under reduced pressure. 5g of the precursor thus obtained was mixed with 200ml of CFC-113, and the mixture was reacted at 0 ℃ for 6 hours by supplying fluorine gas at a concentration of 20% and followed by GC-MS. And after the reaction is finished, adding a 5M potassium hydroxide aqueous solution into the reaction solution until the pH value is neutral, separating out a water phase, concentrating, and freeze-drying to obtain the potassium perfluorocarboxylate. Heating the obtained potassium perfluorocarboxylate to 250 ℃ in a nitrogen atmosphere for thermal decomposition reaction, cooling a fraction receiving bottle by using a dry ice-acetone bath in the thermal decomposition process, and collecting colorless transparent liquid which is a perfluoro (2-methylene-4, 6-dimethyl-1, 3-dioxane) monomer.
Example 5
0.028 mol of monomer, 1% perfluorobenzoyl peroxide (FBPO) was placed in a 25 ml polymerization flask, cooled with liquid nitrogen, degassed in vacuo three times, sealed, stirred at 65 ℃ for 48 hours, and the residual monomer was aspirated off to give a colorless transparent solid in 35% yield. Glass transition temperature TgIt was stable at 138 ℃ and 340 ℃ with a 10% weight loss at 420 ℃.
Example 6
0.028 mol of monomer, 1% bis (4-tert-butylcyclohexyl) peroxydicarbonate, was placed in a 25 ml polymerization flask, cooled with liquid nitrogen, degassed in vacuo three times, sealed and stirred at 65 ℃ for 48 hours. A colorless, transparent solid was obtained in 35% yield. Glass transition temperature TgHigh temp. at 138 deg.C and 340 deg.CThere was a 10% weight loss at 420 ℃.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A fluoromonomer of the structure of formula (I):
2. a fluoropolymer having the structure of formula (II):
wherein n is the number of repeating units and is an integer greater than or equal to zero.
3. A preparation method of a fluorine-containing monomer with a structure shown in a formula (I) is characterized by comprising the following steps:
a) reacting methyl pyruvate with 2, 4-pentanediol to obtain 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxycyclohexane;
b) 2-methyl ester-2, 4, 6-trimethyl-1, 3-dioxane is fluorinated and neutralized to obtain fluorine-containing carboxylic acid alkali metal salt;
c) decomposing the fluorine-containing carboxylic acid alkali metal salt to obtain the monomer with the structure of the formula (I).
4. The method according to claim 3, wherein the molar ratio of methyl pyruvate to 2, 4-pentanediol in step a) is 1: 1; the solvent is selected from one or more of benzene and toluene; the catalyst is one or more selected from p-toluenesulfonic acid and Amberlyst-15 acid resin.
5. The method according to claim 3, wherein the fluorination in step b) is carried out by introducing fluorine gas at a concentration of 10% to 30% and fluorinating the fluorine gas at 0 ℃ to 20 ℃ for 6 to 24 hours.
6. The method according to claim 3, wherein the fluorinated solvent in step b) is selected from one or more of perfluorohexane, perfluorobutyltetrahydrofuran, and 1,1, 2-trichloro-trifluoroethane; the neutralizing alkali is potassium hydroxide or sodium hydroxide neutralization.
7. The preparation method according to claim 3, wherein the decomposition in step c) is specifically: heating to 200-250 deg.C for decomposition.
8. A method for preparing a fluorine-containing polymer with a structure shown in a formula (II), which is characterized by comprising the following steps:
the monomer with the structure of the formula (I) is polymerized under the action of an initiator to obtain the polymer with the structure of the formula (II).
9. The method according to claim 8, wherein the initiator is selected from one or more of perfluorobenzoyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate and perfluorodibutyryl peroxide.
10. The process according to claim 8, wherein the polymerization is in particular: polymerizing for 1-8 hours at 30-65 ℃ under the condition of inert gas.
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| CN110256912A (en) * | 2019-04-30 | 2019-09-20 | 宁波瑞凌新能源科技有限公司 | A kind of radiation refrigeration layer structure, photovoltaic module |
| CN112243450A (en) * | 2018-06-12 | 2021-01-19 | 3M创新有限公司 | Fluoropolymer nanoparticle coating compositions |
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| WO2017069795A1 (en) * | 2015-10-23 | 2017-04-27 | Membrane Technology And Research, Inc. | Gas separation membranes based on fluorinated and perfluorinated polymers |
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| WO2017069795A1 (en) * | 2015-10-23 | 2017-04-27 | Membrane Technology And Research, Inc. | Gas separation membranes based on fluorinated and perfluorinated polymers |
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| CN112243450A (en) * | 2018-06-12 | 2021-01-19 | 3M创新有限公司 | Fluoropolymer nanoparticle coating compositions |
| CN112243450B (en) * | 2018-06-12 | 2023-01-13 | 3M创新有限公司 | Fluoropolymer nanoparticle coating compositions |
| US11866602B2 (en) | 2018-06-12 | 2024-01-09 | 3M Innovative Properties Company | Fluoropolymer compositions comprising fluorinated additives, coated substrates and methods |
| US12018144B2 (en) | 2018-06-12 | 2024-06-25 | 3M Innovative Properties Company | Fluoropolymer coating compositions comprising amine curing agents, coated substrates and related methods |
| CN110256912A (en) * | 2019-04-30 | 2019-09-20 | 宁波瑞凌新能源科技有限公司 | A kind of radiation refrigeration layer structure, photovoltaic module |
| US11781004B2 (en) | 2019-11-04 | 2023-10-10 | 3M Innovative Properties Company | Electronic telecommunications articles comprising crosslinked fluoropolymers and methods |
| CN117843865A (en) * | 2022-10-09 | 2024-04-09 | 宁波嘉玛材料科技有限公司 | Amorphous fluororesin, preparation method and application thereof, light-transmitting oxygen-permeable release film, and preparation method and application thereof |
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