CN110776426B - 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester and preparation method and application thereof - Google Patents
2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000004593 Epoxy Substances 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 229920002313 fluoropolymer Polymers 0.000 claims description 7
- 239000004811 fluoropolymer Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 abstract description 26
- 239000011737 fluorine Substances 0.000 abstract description 26
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000178 monomer Substances 0.000 abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000037048 polymerization activity Effects 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000006184 cosolvent Substances 0.000 abstract description 2
- 150000001266 acyl halides Chemical class 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- -1 perfluoro Chemical group 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000003595 spectral effect Effects 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003480 eluent Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
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- 239000003208 petroleum Substances 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 150000001265 acyl fluorides Chemical class 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 230000007704 transition Effects 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000007924 injection Substances 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012653 anionic ring-opening polymerization Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009439 industrial construction Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
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- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- 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
- C08F112/00—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 aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3314—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic
- C08G65/3315—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic
- C08G65/3317—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group cyclic aromatic phenolic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester, a preparation method and application thereof, wherein the structural formula is as follows:
wherein R is-CH2CH3or-CH ═ CH2And n is an integer of 1 to 14. The fluorine-containing ester is prepared by taking perfluoro epoxy oligomer acyl halide as a substrate and carrying out esterification reaction with p-ethylphenol or p-hydroxystyrene. The compound of the invention has the advantages of simple and efficient preparation method, mild reaction conditions, high yield, simple post-treatment and supercritical CO2Has excellent medium solubility. Wherein, the 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-vinyl phenyl ester is a high fluorine-containing styrene monomer in supercritical CO2The medium free radical polymerization condition is mild, the homogeneity is good, the performance of the polymerization product is excellent, and the monomer also has excellent photo-initiation polymerization activity. The 2-perfluoro epoxy oligomer-p-ethylphenyl tetrafluoropropionate can be used as a precursor of a fluorine-containing monomer and a cosolvent of a polymerization reaction.
Description
Technical Field
The invention belongs to the technical field of polymer chemistry and chemical engineering, and particularly relates to novel 2-perfluoro epoxy oligomer-p-alkyl phenyl tetrafluoropropionate, and a preparation method and application thereof.
Background
The fluorine-containing polymer refers to a polymer in which hydrogen atoms bonded to C-C bonds in a high molecular polymer are partially or completely substituted by fluorine atoms. The fluoropolymer has been widely used in aerospace, industrial construction, machinery, military, electronics, medicine and other fields because of its unique advantages in the 20 th century and the 30 th century. The high-performance polyurethane elastomer has the advantages of small friction coefficient, low surface free energy, good biocompatibility, excellent water resistance, oil resistance, weather resistance, chemical resistance and the like, and can be used for preparing high-performance sealing materials, lubricating materials, medical materials, coating materials, surfactants, elastomers and the like.
The preparation of fluoromonomers is the basis of fluoropolymer material research. The preparation of novel fluoromonomers, the study of the polymerization method of fluoromonomers, the chemical modification of fluoropolymers, and the introduction of fluorine atoms into non-fluoropolymers are four major problems in the study of the synthesis method of fluoropolymers. Hexafluoropropylene oxide oligomer ((HFPO)nN = an integer of 2 to 15) is a specific fluorine-containing polymer, and mainly refers to a polymer with a molecular weight of 300 to 3000 such as a hexafluoropropylene oxide 2 to 15-mer. The most efficient and most commonly used method for preparing hexafluoropropylene oxide oligomers is the anionic ring-opening polymerization of hexafluoropropylene oxide (HFPO).
Supercritical carbon dioxide (scCO)2) Means that both temperature and pressure are above their critical values (T = 31.1)oC, p =7.38 MPa) CO2Fluid, in supercritical state, CO2Has a high density like a liquid and a low viscosity close to that of a gas. In recent years, scCO2The catalyst is considered to be an environment-friendly green polymerization reaction medium due to the unique advantages, and has wide application prospect. Compared with the traditional polymerization medium, the scCO2Has the advantages of no toxicity, no pollution, no combustion, no explosion, no chemical inertia, no chain transfer, low cost and easy operationThe recovery and the critical state are easy to realize, and more importantly, the scCO2The physical and chemical properties of the catalyst can be continuously adjusted by changing the temperature and the pressure, and the unique advantage lays a foundation for strengthening mass transfer and regulating and controlling the reaction process. In addition, scCO2Low viscosity, high diffusion coefficient, better plasticizing effect on the polymer, and removing CO by decompression after the polymerization reaction2No solvent remained in the system. Literature (Macromolecules, 2012, 45, 4907) shows that styrene and most vinyl monomers are present in scCO2Has good solubility, but the oligomer or polymer thereof is in scCO2Has very limited solubility, so that a plurality of monomers are in the scCO2It is difficult to achieve homogeneous or solution polymerization, and as the molecular weight of the polymerization product increases, the homogeneity of the polymerization system further deteriorates. The literature (Green Chemistry, 2015, 17, 4489) shows that (HFPO)nIs so far in scCO2The fluorine-containing organic matter with the best medium solubility can be used as a high-efficiency solubilizing chain or a surface active functional module to introduce specific molecules, so that the scCO content of a target product is remarkably improved2The solubility in (b) improves the homogeneity of the mixed system. Chinese patent CN108329465A discloses a fluorine-containing epoxy oligomer styrene monomer (FEO) with carbonyl connecting wallnCOSt) and preparation method and application thereof, and the method has good selectivity and high yield, and FEOnCOSt in scCO2Intermediate transition pressure (P T) Small size, mild polymerization condition, good homogeneity during polymerization, good performance of the obtained product and no solvent residue, and overall, FEOnCOSt can be applied to scCO2Controllable preparation of high-performance fluorine-containing polymer functional material. However, the technology has the following outstanding disadvantages: firstly, the preparation conditions are harsh, a metal organic reagent method is adopted in the preparation process of a target product, substrates such as p-bromostyrene and the like used in the method are expensive, the reaction needs to be carried out under strict anhydrous and anaerobic conditions and under the protection of inert atmosphere, and the technical route has high cost and is difficult to realize large-scale production due to the factors; secondly, the polymerization activity of the monomers is limitedFEO, a target product thereofnThe COSt molecule contains a carbonyl connecting arm, and the strong electron-withdrawing conjugation effect of the carbonyl of the connecting arm can obviously reduce the electron density of the polymerized end C = C of the fluorine-containing monomer, so that the polymerization reaction activity of the fluorine-containing monomer is reduced, and the polymerization research and further industrial application of the fluorine-containing monomer are limited to a certain extent. For example, FEO2The conversion of COSt at 70 ℃ and 25 MPa for 48 hours was 70%, the molecular weight of the polymer obtained was 23900 g/mol.
Ethylbenzene is an important intermediate or precursor for preparing styrene in petrochemical industry, and is also one of important solvents for synthesizing rubber in polymer chemical industry. But ethylbenzene has poor solubility to fluorine-containing polymers, so that ethylbenzene cannot be used as a solvent for preparing fluorine-containing polymer functional materials such as fluorine-containing styrene and the like. Therefore, consider (HFPO) discovered in earlier studiesnIs introduced into ethylbenzene as a high-efficiency solubilizing chain to design and synthesize a synthetic method in scCO2The precursor of fluorine-containing styrene monomer with excellent dissolving performance or the solvent of fluorine-containing polymerization system, namely fluorine-containing epoxy oligomer ethylbenzene. Chinese patent 2018101653456 discloses a fluorine-containing epoxy oligomer based ethylbenzene (FEO) with carbonyl connecting wallnCOEB) and a method for the production thereof. FEO of the inventionnCOEB in scCO2Pressure of transformation in a mediumP TSmall solubility, good performance, can be fully dispersed and mixed with scCO under lower pressure2Miscible is scCO2-FEOnThe efficient cosolvent of the COSt system can obviously improve the homogeneity of a polymerization reaction system. However, the technology has the following significant disadvantages that the preparation process of the target product also adopts a metal organic reagent method, the substrate such as p-bromoethylbenzene used in the method is expensive, the reaction needs to be carried out under strict anhydrous and anaerobic conditions and under the protection of inert atmosphere, and the cost is too high to realize large-scale production.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect that the styrene-polystyrene system is in scCO2Poor medium solubility, poor controllability of the polymerization process and the disclosed fluorobenzene-containing compoundsThe polymerization activity of ethylene monomer is low, and provides a method for preparing scCO2The 2-perfluoro epoxy oligomer group-tetrafluoropropionic acid p-alkyl phenyl ester with excellent dissolving performance and high polymerization activity in the intermediate has ester group connecting arms.
The invention aims to solve another technical problem of providing a preparation method which is simple to operate for the 2-perfluor epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester.
The invention also aims to solve a technical problem of providing a new application of the 2-perfluor epoxy oligomer-tetrafluoro propionic acid p-alkyl phenyl ester.
The structural formula of the 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester adopted for solving the technical problems is as follows:
wherein R represents-CH2CH3or-CH = CH2And n is an integer of 1 to 14.
The preparation method of the 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester comprises the following steps: adding p-ethylphenol or p-hydroxystyrene and a compound shown in the formula I into a solvent, adding a catalyst and an acid-binding agent, fully stirring and reacting at room temperature to 60 ℃ in an argon atmosphere, reacting for 1-5 h, and then separating and purifying to obtain a target product, wherein R represents-CH2CH3When the target product is designated as FEOnCOOEB, R stands for-CH = CH2When the target product is designated as FEOnCOOSt; the reaction equation is as follows:
in the formula I, X represents-F or-Cl.
In the preparation method, the molar ratio of the p-ethylphenol or the p-hydroxystyrene to the compound of the formula I is preferably 1: 1-1.5.
In the preparation method, the catalyst is any one of N, N-dimethylformamide, N-dimethylacetamide and 4-dimethylaminopyridine, preferably N, N-dimethylformamide, wherein the adding amount of the catalyst is 0.03-0.1% of the molar amount of p-ethylphenol or p-hydroxystyrene.
In the preparation method, the acid-binding agent is any one of triethylamine, pyridine and N, N-dimethylaniline, preferably triethylamine, wherein the addition amount of the acid-binding agent is 0.07-0.2% of the molar amount of p-ethylphenol or p-hydroxystyrene.
In the preparation method, the solvent is any one of dichloromethane, dichloroethane, trichloromethane and trichloroethane.
The invention relates to application of 2-perfluoro epoxy oligomer-p-alkyl phenyl tetrafluoropropionate in preparing a fluorine-containing polymer in a supercritical carbon dioxide system, which comprises the following specific application methods: adding 2-perfluoro epoxy oligomer-tetrafluoropropionic acid p-alkyl phenyl ester and a free radical initiator into a reaction kettle, polymerizing under the conditions that the pressure is 10-30 MPa and the temperature is 50-80 ℃, after the polymerization is finished, closing heating and stopping stirring, reducing the pressure in the reaction kettle to normal pressure by slowly discharging gas after the temperature of the reaction kettle is reduced to room temperature, opening the reaction kettle, and collecting a polymerization product.
The invention has the following advantages:
(1) the preparation method disclosed by the invention is green and efficient, mild in reaction conditions, simple in post-treatment, high in conversion rate and easy to realize large-scale production, and is an effective way for obtaining the novel fluorine-containing monomer.
(2) FEO of the present inventionnCOOEB in scCO2Has small transformation pressure, can be fully dispersed at lower pressure and can be mixed with scCO2Miscible is scCO2-FEOnThe good solvent of the COOSt polymerization system can improve the homogeneity of the polymerization reaction system.
(3) FEO of the present inventionnCOOSt contains an ester-based linking arm, and oxygen in the single bond of the ester-based COO has an electron donating effect of activating a benzene ring, and is transferred to C = C at the polymerization terminal through the benzene ring, so that the C = C electron cloud density increases a radical and the activity of photoinitiated polymerization increases.
(4) FEO of the present inventionnCOOSt in scCO2The method has the advantages of small transition pressure, low polymerization reaction pressure, mild conditions, good homogeneity in the polymerization process, excellent product performance, no solvent residue and applicability to scCO2Controllable preparation of high-performance fluorine-containing polymer functional material.
Drawings
FIG. 1 shows FEO prepared in example 2 at 50 deg.C, 60 deg.C and 70 deg.C2COOEB in scCO2Middle transformation pressure (and its FEO reported in Chinese invention patent 2018101653456)2COEB in scCO2Transition pressure contrast plot in (1).
FIG. 2 shows FEO prepared in example 5 at 50 deg.C, 60 deg.C and 70 deg.C2COOSt in scCO2Middle transformation pressure (and its FEO reported in Chinese invention patent 2018101653456)2COSt in scCO2Transition pressure contrast plot in (1).
Detailed Description
The invention will be further described with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
The preparation method of the 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-ethyl phenyl ester (FEOCOOEB) comprises the following steps:
0.51 g (4.2 mmol) of 4-ethylphenol was charged in a three-necked flask, 20 mL of methylene chloride was added, and 1.99 g (6 mmol) of hexafluoropropylene oxide dimer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3) COF, supplied by Zhejiang Cyclo New fluorine materials Co., Ltd, and designated FEOCOF), after the addition was completed, 0.05 mL (0.0007 mmol) of N, N-Dimethylformamide (DMF) was added, and 0.4 mL (0.003 mmol) of dried triethylamine was slowly added dropwise thereto, and after the addition was completed, the reaction was stirred at 40 ℃ for 2 hours. After the reaction was complete, 20 mL of deionized water was added and extracted with dichloromethane (20 mL. times.3) and combinedThe organic phase was combined with MgSO4Drying, filtering and rotary evaporation to obtain the crude product, which is separated by silica gel column chromatography (using petroleum ether as eluent) to obtain colorless and slightly viscous liquid, namely the target product, with the yield of 99.1 percent and the spectral data as follows:
FT-IR (liquid membrane method): 3041, 2978, 2938, 2880, 1796, 1600, 1503, 1458, 1380-1000, 810 cm-1。
1H NMR（400 MHz, CDCl3）：7.25（d, 2ArH），7.05（d, 2ArH），2.67（q, 2H），1.25（t, 3H）。
13C NMR（400 MHz，CDCl3）：157.76，147.55，143.78，129.31，120.05，99.00～130.00，28.35，15.45 ppm。
HRMS（ESI）：[M+Na]= 457.0277。
Example 2
Preparing 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-ethyl phenyl ester (FEO) with the structural formula2COOEB), the specific preparation method thereof is as follows:
0.51 g (4.2 mmol) of 4-ethylphenol was charged in a three-necked flask, 20 mL of methylene chloride was added thereto, and 2.99 g (6 mmol) of hexafluoropropylene oxide trimer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3)CF2OCF(CF3) COF, available from New fluorine materials, Inc. of Zhejiang province, and designated FEO2COF), adding 0.1 mL (0.0013 mmol) of DMF after the addition is finished, slowly dropwise adding 0.5 mL (0.0036 mmol) of dried triethylamine, and stirring for reacting for 2 h at 40 ℃ after the dropwise addition is finished. After the reaction was complete, 25 mL of deionized water was added and extracted with dichloromethane (25 mL. times.3), the organic phases were combined and MgSO4Drying, filtering, rotary evaporating to obtain crude product, separating with silica gel column chromatography (with petroleum ether as eluent) to obtain colorless slightly viscous liquid, which is the target productThe ratio was 99.5%, and the spectral data were as follows:
FT-IR (liquid film method): 3041, 2978, 2938, 2880, 1796, 1600, 1503, 1458, 1380-1000, 810 cm-1。
1H NMR（400 MHz, CDCl3）：7.25（d, 2ArH），7.05（d, 2ArH）， 2.67（q, 2H），1.25（t, 3H）。
13C NMR（400 MHz，CDCl3）：157.76，147.55，143.78，129.31，120.05，99.00～130.00，28.35，15.45 ppm。
HRMS（ESI）：[M+Na]= 623.0132。
Example 3
Preparing 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-ethyl phenyl ester (FEO) with the structural formula3COOEB), the specific preparation method thereof is as follows:
under an argon atmosphere, 0.51 g (4.2 mmol) of 4-ethylphenol was put in a three-necked flask, 30 mL of dichloroethane was added, and 3.98 g (6 mmol) of hexafluoropropylene oxide tetramer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3) COF, available from New fluorine materials, Inc. of Zhejiang province, and designated FEO3COF), adding 0.15 mL (0.002 mmol) of DMF after the addition is finished, slowly dropwise adding 0.6 mL (0.0044 mmol) of dried triethylamine, and stirring for reaction at 50 ℃ for 2 h after the dropwise addition is finished. After the reaction was complete, 40 mL of deionized water was added and extracted with dichloromethane (30 mL. times.3), the organic phases were combined and MgSO4Drying, filtering and rotary evaporation to obtain the crude product, which is separated by silica gel column chromatography (using petroleum ether as eluent) to obtain colorless and slightly viscous liquid, namely the target product, with the yield of 99.0 percent and the spectral data as follows:
FT-IR (liquid film method): 3041, 2978, 2938, 2880, 1796, 1600，1503，1458，1380～1000，810 cm-1。
1H NMR（400 MHz, CDCl3）：7.25（d, 2ArH），7.05（d, 2ArH），2.67（q, 2H），1.25（t, 3H）。
13C NMR（400 MHz，CDCl3）：157.76，147.55，143.78，129.31，120.05，99.00～130.00，28.35，15.45 ppm。
HRMS（ESI）：[M+Na]=788.9971。
Example 4
Preparing 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-ethyl phenyl ester (FEO) with the structural formula14COOEB), the specific preparation method thereof is as follows:
under an argon atmosphere, 0.51 g (4.2 mmol) of 4-ethylphenol was put in a three-necked flask, 30 mL of trichloroethane was added, and 15.0 g (6 mmol) of hexafluoropropene oxide pentadecamer (CF) having an acid chloride terminal group was added under stirring3CF2CF2O(CF(CF3)CF2O)13CF(CF3) COCl, denoted FEO14COCl), then 0.15 mL (0.002 mmol) of DMF is added, and 1.0 mL (0.007 mmol) of dried triethylamine is slowly added dropwise, after the addition is finished, the reaction is stirred at 60 ℃ for 5 h. After completion of the reaction, 80 mL of deionized water was added and extracted with dichloromethane (100 mL. times.3), and the organic phases were combined and MgSO4Drying, filtering and rotary evaporation to obtain a crude product, and separating the crude product by silica gel column chromatography (using petroleum ether as an eluent) to obtain a colorless and slightly viscous liquid, namely the target product, and the spectral data are as follows:
FT-IR (liquid membrane method): 3040, 2978, 2938, 2880, 1796, 1600, 1503, 1458, 1380-1000, 810 cm-1。
Example 5
The preparation method of 2-perfluoro epoxy oligomer group-tetrafluoro propionic acid p-vinyl phenyl ester (FEOCOOSt) comprises the following steps:
under an argon atmosphere, 0.50 g (4.2 mmol) of 4-hydroxystyrene was charged into a three-necked flask, 20 mL of methylene chloride was added, and 1.99 g (6 mmol) of hexafluoropropylene oxide dimer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3) COF, supplied by Funiu New Fluoromaterials Co., Ltd., Zhejiang province, and designated FEOCOF), after the addition was completed, 0.05 mL (0.0007 mmol) of DMF was added, and 0.4 mL (0.003 mmol) of dried triethylamine was slowly added dropwise thereto, and after the addition was completed, the reaction was stirred at 40 ℃ for 4 hours. After the reaction was complete, 20 mL of deionized water was added and extracted with dichloromethane (20 mL. times.3), the organic phases were combined and MgSO4Drying, filtering and rotary evaporation to obtain the crude product, which is separated by silica gel column chromatography (using petroleum ether as eluent) to obtain colorless and slightly viscous liquid, namely the target product, with the yield of 99.5 percent and the spectral data as follows:
FT-IR (liquid membrane method): 3098, 1796, 1640, 1605, 1503, 1350-1100, 1030, 986, 908, 820 cm-1。
1H NMR（400 MHz, CDCl3）：7.45（d, 2ArH），7.09（d, 2ArH），6.69（dd, CH=），5.72（d, -CHH），5.29（d, -CHH）。
13C NMR（400 MHz，CDCl3）：157.51，148.91，137.15，135.39，127.65，120.40，115.19，99.00～125.00 ppm。
HRMS（ESI）：[M+Na]=455.0110。
Example 6
Preparing 2-perfluoro epoxy oligomer group-tetrafluoropropionic acid p-vinylphenyl ester (FEO) with the structural formula2COOSt), the specific preparation method is as follows:
under an argon atmosphere, 0.50 g (4.2 mmol) of 4-hydroxystyrene was charged into a three-necked flask, 20 mL of dichloroethane was added, and 2.99 g (6 mmol) of hexafluoropropylene oxide trimer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3)CF2OCF(CF3) COF, available from New fluorine materials, Inc. of Zhejiang province, and designated FEO2COF), adding 0.1 mL (0.0013 mmol) of DMF after the addition is finished, slowly dropwise adding 0.6 mL (0.0044 mmol) of dried triethylamine, and stirring for reaction at 50 ℃ for 4 h after the dropwise addition is finished. After the reaction was complete, 30 mL of deionized water was added and extracted with dichloromethane (30 mL. times.3), the organic phases were combined and MgSO4Drying, filtering and rotary evaporation to obtain the crude product, which is separated by silica gel column chromatography (using petroleum ether as eluent) to obtain colorless and slightly viscous liquid, namely the target product, with the yield of 99.0 percent and the spectral data as follows:
FT-IR (liquid membrane method): 3098, 1796, 1640, 1605, 1503, 1350-1100, 1030, 986, 908, 820 cm-1。
1H NMR（400 MHz, CDCl3）：7.45（d, 2ArH），7.09（d, 2ArH），6.69（dd, CH=），5.72（d, -CHH），5.29（d, -CHH）。
13C NMR（400 MHz，CDCl3）：157.51，148.91，137.15，135.39，127.65，120.40，115.19，99.00～125.00 ppm。
HRMS（ESI）：[M+Na]=620.9973。
Example 7
Preparing 2-perfluoro epoxy oligomer group-tetrafluoropropionic acid p-vinylphenyl ester (FEO) with the structural formula3COOSt), the specific preparation method is as follows:
under an argon atmosphere, 0.50 g (4.2 mmol) of 4-hydroxystyrene was chargedInto a three-necked flask, 20 mL of methylene chloride was charged, and 3.98 g (6 mmol) of hexafluoropropylene oxide tetramer (CF) having an acyl fluoride terminal group was added under stirring3CF2CF2OCF(CF3)CF2OCF(CF3)CF2OCF(CF3) COF, available from New fluorine materials, Inc. of Zhejiang province, and designated FEO3COF), then adding 0.15 mL (0.0002 mmol) of DMF after the addition is finished, slowly dropwise adding 0.8 mL (0.006 mmol) of dried triethylamine, and after the dropwise addition is finished, stirring the reaction at 40 ℃ for 4 h. After the reaction was complete, 30 mL of deionized water was added and extracted with dichloromethane (30 mL. times.3), the organic phases were combined and MgSO4Drying, filtering and rotary evaporation to obtain a crude product, which is separated by silica gel column chromatography (using petroleum ether as an eluent) to obtain a colorless and slightly viscous liquid, namely the target product, with the yield of 98.0 percent and the spectral data as follows:
FT-IR (liquid membrane method): 3098, 1796, 1640, 1605, 1503, 1350-1100, 1030, 986, 908, 820 cm-1。
1H NMR（400 MHz, CDCl3）：7.45（d, 2ArH），7.09（d, 2ArH），6.69（dd, CH=），5.72（d, -CHH），5.29（d, -CHH）。
13C NMR（400 MHz，CDCl3）：157.51，148.91，137.15，135.39，127.65，120.40，115.19，99.00～125.00 ppm。
HRMS（ESI）：[M+Na]=786.9818。
The FEO prepared in example 2 was measured at 50 deg.C, 60 deg.C and 70 deg.C respectively using a high pressure in situ infrared spectroscopy monitoring system (HP ATR-FT MIR) reported in the literature (Macromolecules, 2012, 45, 4907-2COOEB and FEO prepared in example 52COOSt in scCO2Solvent dispersion process in medium. The measured transformation pressure result is compared with the FEO reported in the Chinese invention patent 20181016534562COEB and FEO2The transition pressure plots of COSt under the same conditions are shown in FIGS. 1 and 2. The results showed that FEO was produced under the above temperature conditions2COOEB in scCO2Having in the medium a similar FEO2The excellent solubility of COEB is within 1 MPa of the transition pressure value of the COEB at the same temperature, and the FEO2COOSt in scCO2Having in the medium a similar FEO2The excellent solubility of COSt, both transition pressures are approximately equal at 60 ℃. In addition, FEOCOOEB prepared in example 1 and FEO prepared in example 3 were measured at 60 ℃ and 70 ℃ respectively in the same manner3COOEB in scCO2Solvation dispersion process in the medium. The results show that both monomers can react with scCO under mild conditions at each of the above temperatures2The medium is miscible, the maximum pressure is not more than 14 MPa, indicating that the medium is in scCO2Excellent solubility in the medium.
Example 8
FEO prepared in example 52COOSt in scCO2Use of a system for the preparation of fluoropolymers
1. Free radical initiated polymerization
The stainless steel autoclave equipped with a sapphire visible window was heated to a target temperature of 70 ℃. Then filling argon into the reaction kettle, vacuumizing, and repeating the operation for three times to remove residual oxygen, moisture and volatile substances in the reaction kettle. 9.02 g (0.015 mol) of FEO is added into a high-pressure reaction kettle through a sample injection sample tube2COOSt, then quickly filling CO into the high-pressure reaction kettle2The stirring was turned on to promote the monomer dissolution to become homogeneous. 0.05 g (0.0003 mol) of Azobisisobutyronitrile (AIBN), an initiator of which was previously charged in a high-pressure sample injection apparatus, was charged with high-pressure CO2The mixture is flushed into a high-pressure reaction kettle, and timing is started. Continuously stirring and supplementing CO2The pressure in the high-pressure reaction kettle is kept at 25.0 MPa for polymerization, and the polymerization reaction time is 12 h. And after the polymerization is finished, closing heating and stirring, slowly discharging gas and reducing pressure to normal pressure after the high-pressure reaction kettle is cooled to room temperature, starting the high-pressure reaction kettle, and collecting a polymerization product. The conversion of this polymerization was measured to be greater than 99%. Spectral data are as follows:
FT-IR (liquid membrane method): 2928, 1978, 1603, 1505, 1453, 1384, 1350-1100, 1034, 994, 811 cm-1。
1H NMR（400 MHz, CDCl3）：7.04（d, 2ArH），6.78（d, 2ArH），1.0～2.5（-CH-CH2-）。
The molecular weight of the polymer was determined by MALDI-TOF method reported in the literature (Macromolecules, 2012, 45, 4907-4919)M nIt was 96800 g/mol.
2. Ultraviolet light initiated polymerization
0.055 g of benzophenone was put into a three-necked flask, argon gas was introduced into the flask, followed by vacuum evacuation, and this operation was repeated three times alternately to remove volatile substances such as residual oxygen in the flask. 18.04 g (0.03 mol) FEO was added to the flask via syringe2COOSt, then adding 36 mL of toluene, and after the dropwise addition, placing the mixture under a 365 nm ultraviolet lamp to stir for 6 h at normal temperature. After the polymerization is finished, the polymer is dissolved in 1,1, 2-trifluorotrichloroethane, then dichloromethane is used for precipitating the polymer, and a polymerization product is collected and dried for characterization. Spectral data are as follows:
FT-IR (liquid membrane method): 2928, 1978, 1603, 1505, 1453, 1384, 1350-1100, 1034, 994, 811 cm-1。
1H NMR（400 MHz, CDCl3）：7.04（d, 2ArH），6.80（d, 2ArH），1.0～2.5（-CH-CH2-）。
The molecular weight of the polymer was determined by MALDI-TOF method reported in the literature (Macromolecules, 2012, 45, 4907-4919)M nIt was 22046 g/mol.
Claims (8)
1. A preparation method of 2-perfluoro epoxy oligomer-tetrafluoro propionic acid p-alkyl phenyl ester is characterized by comprising the following steps: adding p-hydroxystyrene and a compound shown in the formula I into a solvent, adding a catalyst and an acid-binding agent, stirring the obtained mixture at room temperature to 60 ℃ in an argon atmosphere, reacting for 1-5 hours, separating and purifying to obtain a target product, wherein the reaction equation is as follows:
wherein R represents-CH = CH2N is an integer of 1-14, and X represents-F or-Cl;
the catalyst is any one of N, N-dimethylformamide, N-dimethylacetamide and 4-dimethylaminopyridine; the acid-binding agent is any one of triethylamine, pyridine and N, N-dimethylaniline.
2. The method for producing p-alkylphenyl 2-perfluoroepoxy oligomer-tetrafluoropropionate according to claim 1, wherein: the molar ratio of the p-hydroxystyrene to the compound of the formula I is 1: 1-1.5.
3. The method for producing p-alkylphenyl 2-perfluoroepoxy oligomer-tetrafluoropropionate according to claim 1, wherein: the catalyst is N, N-dimethylformamide.
4. The process for producing p-alkylphenyl 2-perfluoroepoxy oligomer-based-tetrafluoropropionate according to claim 1 or 3, wherein: the addition amount of the catalyst is 0.03-0.1% of the molar amount of the p-hydroxystyrene.
5. The method for producing p-alkylphenyl 2-perfluoroepoxy oligomer-tetrafluoropropionate according to claim 1, wherein: the acid-binding agent is triethylamine.
6. The process for producing p-alkylphenyl 2-perfluoroepoxy oligomer-based-tetrafluoropropionate according to claim 1 or 5, wherein: the addition amount of the acid-binding agent is 0.07-0.2% of the molar amount of the p-hydroxystyrene.
7. The method for producing p-alkylphenyl 2-perfluoroepoxy oligomer-tetrafluoropropionate according to claim 1, wherein: the solvent is any one of dichloromethane, dichloroethane, trichloromethane and trichloroethane.
8. Use of the 2-perfluoroepoxy oligomer-p-alkyl phenyl tetrafluoropropionate prepared by the method of claim 1 in the preparation of a fluoropolymer in a supercritical carbon dioxide system.
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