CN111606778A - Catalytic synthesis method of hexafluoropropylene oligomer - Google Patents
Catalytic synthesis method of hexafluoropropylene oligomer Download PDFInfo
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- CN111606778A CN111606778A CN202010604952.XA CN202010604952A CN111606778A CN 111606778 A CN111606778 A CN 111606778A CN 202010604952 A CN202010604952 A CN 202010604952A CN 111606778 A CN111606778 A CN 111606778A
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- hexafluoropropylene
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- alkali metal
- oligomer
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- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 8
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 alkali metal salt Chemical class 0.000 claims abstract description 35
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 34
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 8
- 229920000151 polyglycol Polymers 0.000 claims abstract description 7
- 239000010695 polyglycol Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000013638 trimer Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 claims description 4
- PBVZTJDHQVIHFR-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C(F)C(F)(F)F.FC(F)=C(F)C(F)(F)F PBVZTJDHQVIHFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- QUPYHCHUQVNFJW-UHFFFAOYSA-M cesium;thiocyanate Chemical compound [Cs+].[S-]C#N QUPYHCHUQVNFJW-UHFFFAOYSA-M 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 29
- 239000011737 fluorine Substances 0.000 abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 16
- UAFOIVDGAVVKTE-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-octadecafluoronon-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAFOIVDGAVVKTE-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 150000003983 crown ethers Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 239000000539 dimer Substances 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000006384 oligomerization reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000004714 phosphonium salts Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical compound N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000002939 oilproofing Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
Abstract
The invention provides a catalytic synthesis method of hexafluoropropylene oligomer. The method comprises the following steps: hexafluoropropylene is used as raw material, alkali metal salt is used as main catalyst, polyglycol fluoroether is used as auxiliary catalyst, in polar aprotic solvent, 0-130oReacting at the temperature of C for 0.5 to 5 hours to obtain the hexafluoropropylene oligomer; the main catalyst comprises: auxiliary catalyst: the mass ratio of the polar aprotic solvent is 1:0.1-10: 10-50. The invention has the following beneficial effects: the adoption of the fluorine ether of polyethylene glycol can solubilize the alkali metal salt, thereby promoting the high conversion of hexafluoropropylene, and simultaneously the intermiscibility of the fluorine ether of polyethylene glycol and hexafluoropropylene is stronger than that of polyethylene glycol, so that the selectivity of hexafluoropropylene tripolymer (perfluorononene) is high. The invention also has the following beneficial effects: the main catalyst and the auxiliary catalyst are combined simply and efficiently, the auxiliary catalyst is cheap and easy to obtain, the catalyst and the solvent are convenient to recover, and the recovered catalyst can be directly usedSimple operation and less three wastes.
Description
Technical Field
The invention relates to a preparation method of hexafluoropropylene oligomer, in particular to a preparation method of hexafluoropropylene oligomer with the hexafluoropropylene tripolymer mass content of more than 95%.
Background
The hexafluoropropylene oligomer mainly comprises hexafluoropropylene dimer and trimer, and can be obtained quantitatively through oligomerization of hexafluoropropylene monomer. The fluorine atom in the hexafluoropropylene completely replaces a hydrogen atom, and the extremely strong electronegativity of the fluorine atom enables a C-F bond to have extremely large bond energy, so that hexafluoropropylene dimers and trimers have good thermal stability and chemical stability. Hexafluoropropylene dipolymer and tripolymer have various isomerous isomers, and because the hexafluoropropylene dipolymer and the tripolymer both contain double bonds, various fluorine-containing derivatives can be further prepared by reaction, and the derivatives can be used as medicines, pesticide intermediates, high-efficiency fire extinguishing agents, fluorine-containing surfactants, inert liquids, water and oil proofing aids, solvents, fluorine-containing polymer monomers and the like. Therefore, the development and utilization of hexafluoropropylene oligomers and derivatives thereof are of great practical significance.
Hexafluoropropylene trimer having a relative molecular mass of 450.07 and a molecular formula of C9F18The three structural forms of T-1, T-2 and T-3 are total, and the boiling point is between 110 and 115 ℃. One main application of hexafluoropropylene trimer is fluorosilicone modified polyurethane which is prepared from perfluoroolefin, hydroxyl silicone oil, ethylene oxide and diisocyanate serving as raw materials, can be applied to waterproof and oil-repellent treatment of leather, and can improve softness and smoothness.
The fluorine chemical product belongs to the development of new materials which cannot be replaced by the development of high-tech industries and advanced manufacturing industries. Worldwide fluorine industry has formed a competitive format dominated by multinational groups such as DuPont, Solvay, Japan. Perfluoroolefin is used as a raw material, the extension is continuously expanded, a fluorine-containing chemical product tree can be formed, and the downstream high-end application is wide.
At present, the intellectual property protection of hexafluoropropylene oligomerization process is mainly carried out around the development of catalysts for activating perfluoroolefin double bonds. The catalyst generally comprises fluoride salt or (thiocyanate) of alkali metal as a main catalyst, organic amine, quaternary ammonium salt, quaternary phosphonium salt or fluorine-containing tertiary amine as a cocatalyst system, and crown ether as a catalytic promoter. Japan Central glass Co., Ltd. (US 4042638) performs C with KF + crown ether system3F6The trimerization reaction of (CN 103752342) adopts KF +2, 2-bipyridine + succinic acid complex loaded by resin-based spherical active carbon as a catalyst for oligomerization. Zhejiang industrial university (CN 101020620) takes alkali metal fluoride as a main catalyst and organic alkali and polyether as auxiliary catalysts, and carries out trimerization reaction by two-stage pressurization. In addition, KCN, KSCN or KOCN is used as an oligomerization catalyst by the company 3M in the United states (CN 1056362), and the selectivity of the product, such as the ratio of dimerization and trimerization, can be regulated by matching with a solvent. On the basis, the Shandong Yue company (CN 1944360) adopts alkali metal cyanate and thiocyanate to carry out oligomerization. The co-catalysis of fluorinated tertiary amines is reported by Thomas Martinni, Germany (US 3917724), DuPont (US 2918501) using metal fluorides such as KF in combination with quaternary ammonium compounds, and Imperial chemical (US 4780559) using fluorinated quaternary phosphonium fluorinating agents for oligomerization.
The above patent reports generally use alkali metal fluoride or cyanate as the main catalyst and crown ether as the catalyst promoter. Crown ethers are a class of macrocyclic polyethers separated from each other by four to about twenty oxygen atoms by two or more carbon atoms, which form stable complexes with alkali and alkaline earth metal cations, wherein the cation is surrounded by the oxygen atoms of the macrocyclic polyether, the cation is received into the polar hydrophilic cavity of the ether molecule, and the exterior of the molecule is lipophilic. This effect is limited to cyclic compounds and is referred to as a macrocyclic effect. By forming complexes with macrocyclic polyethers, inorganic salts can be made soluble in organic solvents, in the case of acyclic polyethers, they are usually practically insoluble therein. Complexation of the cation greatly increases the dissociation of the ion pair between the cation and the anion.
However, the price of crown ether is significantly higher than that of the main catalyst, and the high cost limits the industrial application of the compound. Polyethylene glycol has a molecular structure similar to crown ether, and oxygen atoms in the molecular chain are separated from each other by two carbon atoms to form long-chain polyether. The price of polyethylene glycol is much lower than that of crown ether. The terminal alcoholic hydroxyl group of the polyethylene glycol can react with alkyl with an active functional group or olefin with an active double bond to obtain polyethylene glycol alkyl ether. US4113649 discloses that polyethylene glycol alkyl ethers can solubilize alkali metal salts, wherein it is required that the number of oxygen atoms in the molecular chain is at least greater than 6. The reaction of polyethylene glycol and fluorine-containing olefin can obtain polyethylene glycol fluorine-containing alkyl ether (polyethylene glycol fluorine ether for short). The polyethylene glycol fluoroether obtained by the reaction of polyethylene glycol and fluorine-containing olefin has lower production cost and price than crown ether for enterprises producing or processing fluorine-containing olefin.
In the invention, the expensive crown ether is replaced by the polyethylene glycol fluoroether, the alkali metal salt can be well dissociated by utilizing the polyethylene glycol fluoroether so as to provide anion, and the fluorine-containing phase can promote the dissolution and reaction of hexafluoropropylene, and the like, and the fluorine-containing polyether is used as an auxiliary catalyst of an alkali metal salt main catalyst and is used for the activation polymerization of fluorine-containing olefin, so that the good conversion rate and the selectivity of perfluorononene can be obtained. The catalyst combination can be repeatedly used, and has low cost and high economical efficiency.
Disclosure of Invention
The invention aims to provide a preparation method of hexafluoropropylene oligomer, which has simple reaction conditions, low cost and high trimer yield.
In general, the oligomerization of hexafluoropropylene usually uses fluoride or (thio) cyanate of alkali metal as main catalyst, organic amine, quaternary ammonium salt, quaternary phosphonium salt or fluorine-containing tertiary amine as cocatalyst system, crown ether as catalyst promoter. Crown ethers help to promote the dissociation of alkali metal salts in solvents, but the price of crown ethers is often high, the high cost limits the industrial application of crown ether compounds, and the cost of hexafluoropropylene oligomerization is increased. In addition, organic amine, quaternary ammonium salt, quaternary phosphonium salt or fluorine-containing tertiary amine is generally used as a cocatalyst in the reaction to improve the catalytic activity, so that the catalyst cost of the reaction is further increased.
If a high-efficiency binary catalyst with lower cost can be used to replace the three-way catalyst system, the catalytic performance can be expected to be improved, the process operation is simplified, and the production cost is reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a catalytic synthesis method of hexafluoropropylene oligomer. The method comprises the following steps: hexafluoropropylene is used as raw material, and alkali metal or alkaline earth metal fluoride is used as main catalystThe preparation, polyglycol fluoroether as assistant catalyst, is reacted in polar non-proton solvent at 0-130 deg.coAnd C, reacting for 0.5-5 hours to obtain the hexafluoropropylene oligomer.
The invention adopts the polyethylene glycol fluoroether to replace expensive crown ether, utilizes the performance that the polyethylene glycol fluoroether can well dissociate alkali metal salt to provide anions and a fluorine-containing phase to promote the dissolution and reaction of hexafluoropropylene, and uses the fluorine-containing polyether as an auxiliary catalyst of an alkali metal salt main catalyst for the activation polymerization of fluorine-containing olefin, thereby obtaining good conversion rate and selectivity of perfluorononene. The terminal alcoholic hydroxyl group of the polyethylene glycol can react with alkyl with an active functional group or olefin with an active double bond to obtain polyethylene glycol alkyl ether. The reaction of polyethylene glycol and fluorine-containing olefin can obtain polyethylene glycol fluorine-containing alkyl ether, namely polyethylene glycol fluorine-containing ether. The polyethylene glycol fluoroether obtained by the reaction of polyethylene glycol and fluorine-containing olefin has lower production cost and price than crown ether for enterprises producing or processing fluorine-containing olefin.
The alkali metal salts of the present invention include, but are not limited to, one of the following or a mixture of two or more thereof: NaF; KF, CsF; NaSCN, NaOCN, NaCN; KSCN, KOCN, KCN; CsSCN, CsOCN, CsCN.
The polyethylene glycol fluoroether is open-chain polyether with the following general formula: RO (CH)2CH2O) nR' having at least 7 oxygen atoms separated from each other by 2 carbon atoms, and wherein n =6 and above, e.g. preferably 6-45. R and R' may be the same or different, and when they are the same, both represent-CF2-CFH-CF3. When the two are different, R represents-CF2-CFH-CF3R ' may be branched or straight-chain alkyl having 1 to 20, preferably 1 to 15, carbon atoms, for example methyl, ethyl, n-propyl, sec-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, octyl, decyl, dodecyl, 2-ethylhexyl, etc., R ' may also be cyclohexyl moieties having 3 to 15, preferably 5 to 12, carbon atoms, for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl, R ' may also beAre aryl moieties having 6 and greater than 6 carbon atoms such as phenyl, tolyl, naphthyl and the like.
The alkali metal salt and the polyglycol fluoroether have the following properties when the alkali metal salt and the polyglycol fluoroether occur simultaneously: if desired, alkali metal salts can be dissolved in a solvent (e.g., an organic solvent) with the aid of a fluoroether of polyethylene glycol to obtain a very reactive anion from the salt and for dissolving alkali metals similar to macrocyclic ethers, often even superior thereto.
The polar aprotic solvent of the present invention includes, but is not limited to, one of the following or a mixture of two or more thereof: acetonitrile, dimethyl sulfoxide, dimethylformamide, ethylene glycol dimethyl ether.
The reaction temperature range of the invention is 0 to 130oC, the preferred reaction temperature is 100-120-oC。
The reaction time in the present invention is 0.5 to 5 hours, preferably 1 to 3 hours.
The hexafluoropropylene oligomer at least comprises one or two of hexafluoropropylene dimer and/or hexafluoropropylene trimer.
The mass ratio of the catalyst to the solvent is as follows: auxiliary catalyst: the mass ratio of the polar aprotic solvent is 1:0.1-10:10-50, preferably 1:1-5: 20-40.
The invention has the following beneficial effects: the adoption of the fluorine ether of polyethylene glycol can solubilize the alkali metal salt, thereby promoting the high conversion of hexafluoropropylene, and simultaneously the intermiscibility of the fluorine ether of polyethylene glycol and hexafluoropropylene is stronger than that of polyethylene glycol, so that the selectivity of hexafluoropropylene tripolymer (perfluorononene) is high. The invention also has the following beneficial effects: the main catalyst and the auxiliary catalyst are combined simply and efficiently, the auxiliary catalyst is cheap and easy to obtain, the catalyst and the solvent are convenient to recover, the recovered catalyst can be directly used, the operation is simple, and the three wastes are less.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
3 g of KF and 2 g of polyethylene glycol hexafluoropropylene ether were weighed and dissolved in 30 ml of N, N-dimethylformamide solution. The solution is put in a sealed stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, after the sealed kettle is covered, a vacuumizing device is connected to remove air in the kettle, nitrogen is introduced into the kettle, the kettle is vacuumized again to ensure that the pressure in the kettle is zero, and the air exchange operation is carried out for three times. Heating the reaction kettle to 100 DEGoC activation for 1 hour, then at 100oHexafluoropropylene was bubbled through for 40 minutes at C, at which point 184.5 grams of hexafluoropropylene were bubbled through. After the gas is filled, the reaction is continued for 2 hours, and then the reaction is cooled, and a gas release valve is opened to obtain a brownish red liquid product. After washing with water 3 times, drying and distillation 175.0 g of a colorless liquid product was obtained, i.e. the yield of the obtained oligomer was 94.85%. And (3) rectifying to separate a dimer and a trimer, wherein the mass fractions of the dimer and the trimer are 12.3% and 87.7% respectively.
Example 2:
3 g of KOCN and 2 g of polyethylene glycol hexafluoropropylene ether were weighed out and dissolved in 30 ml of N, N-dimethylformamide solution. The solution is put in a sealed stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, after the sealed kettle is covered, a vacuumizing device is connected to remove air in the kettle, nitrogen is introduced into the kettle, the kettle is vacuumized again to ensure that the pressure in the kettle is zero, and the air exchange operation is carried out for three times. Heating the reaction kettle to 100 DEGoC was activated for 1 hour. Then at 100oHexafluoropropylene was bubbled through for 40 minutes at temperature C, whereupon 170.1 grams of hexafluoropropylene were bubbled through. After the gas is filled, the reaction is continued for 2 hours, and then the reaction is cooled, and a gas release valve is opened to obtain a brownish red liquid product. After washing with water 3 times, drying and distillation 147.8 g of a colorless liquid product were obtained, i.e. the yield of the obtained oligomer was 86.89%. And (3) rectifying to separate a dimer and a trimer, wherein the mass fractions of the dimer and the trimer are 28.2% and 71.8%, respectively.
Example 3:
3 g of KF and 2 g of polyethylene glycol hexafluoropropylene ether were weighed and dissolved in 30 ml of dimethyl sulfoxide solution. The solution is placed in a seal with a polytetrafluoroethylene liningClosing the stainless steel high-pressure reaction kettle, covering and sealing, connecting to a vacuumizing device, removing air, introducing nitrogen, vacuumizing again to ensure that the pressure in the kettle is zero, and performing ventilation operation for three times. Heating the reaction kettle to 100 DEGoC was activated for 1 hour. Then at 100oHexafluoropropylene was bubbled through for 40 minutes at temperature C, whereupon 180.3 grams of hexafluoropropylene were bubbled through. After the gas is filled, the reaction is continued for 2 hours, and then the reaction is cooled, and a gas release valve is opened to obtain a brownish red liquid product. After washing with water 3 times, drying and distillation, 172.5 g of a colorless liquid product were obtained, i.e., the yield of the obtained oligomer was 95.67%. And (3) rectifying to separate a dimer and a trimer, wherein the mass fractions of the dimer and the trimer are 9.1% and 90.9%, respectively.
Example 4:
3 g of KF and 2 g of polyethylene glycol hexafluoropropylene ether are weighed and dissolved in 30 ml of acetonitrile solution. The solution is put in a sealed stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, after the sealed kettle is covered, a vacuumizing device is connected to remove air in the kettle, nitrogen is introduced into the kettle, the kettle is vacuumized again to ensure that the pressure in the kettle is zero, and the air exchange operation is carried out for three times. Cooling the reaction kettle to 10 DEGoAnd C, introducing hexafluoropropylene at the temperature for 40 minutes, wherein 103.2 grams of hexafluoropropylene is introduced. After the gas was filled, the temperature was raised to 60 deg.CoAnd C, continuing to react for 2 hours, cooling, and opening a deflation valve to obtain a brownish red liquid product. After washing with water 3 times, drying and distillation, 78.6 g of a colorless liquid product were obtained, i.e., the yield of the obtained oligomer was 76.16%. And (3) rectifying to separate a dimer and a trimer, wherein the mass fractions of the dimer and the trimer are 95.2% and 4.8%, respectively.
Example 5:
3 g of KF and 2 g of diethylene glycol monomethyl ether hexafluoropropene ether are weighed and dissolved in 30 ml of N, N-dimethylformamide solution. The solution is put in a sealed stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, after the sealed kettle is covered, a vacuumizing device is connected to remove air in the kettle, nitrogen is introduced into the kettle, the kettle is vacuumized again to ensure that the pressure in the kettle is zero, and the air exchange operation is carried out for three times. Heating the reaction kettle to 100 DEGoC was activated for 1 hour. Then at 100oIntroducing hexafluoropropylene at the temperature of C for 40 minutes, and introducingHexafluoropropylene was added to 52.3 grams. After the gas is filled, the reaction is continued for 2 hours, and then the reaction is cooled, and a gas release valve is opened to obtain a brownish red liquid product. After washing with water 3 times, drying and distillation, 1.4 g of a colorless liquid product was obtained, i.e., the yield of the obtained oligomer was 2.68%. And (3) rectifying to separate a dimer and a trimer, wherein the mass fractions of the dimer and the trimer are 56.2 percent and 43.8 percent respectively.
Claims (9)
1. The invention provides a catalytic synthesis method of hexafluoropropylene oligomer, which comprises the following steps: hexafluoropropylene is used as raw material, alkali metal salt is used as main catalyst, polyglycol fluoroether is used as auxiliary catalyst, in polar aprotic solvent, at reaction temperature of 0-130 deg.coAnd C, reacting for 0.5-5 hours to obtain the hexafluoropropylene oligomer.
2. The alkali metal salt of claim 1, wherein the alkali metal salt comprises but is not limited to one of the following or a mixture of two or more thereof: NaF; KF, CsF; NaSCN, NaOCN, NaCN; KSCN, KOCN, KCN; CsSCN, CsOCN, CsCN.
3. The polyglycol fluoroether of claim 1, which is an open chain polyether having the formula: RO (CH)2CH2O) nR' having at least 7 oxygen atoms separated from each other by 2 carbon atoms and wherein n =6 and above, such as preferably 6-45; r and R' may be the same or different, and when they are the same, both represent-CF2-CFH-CF3(ii) a When the two are different, R represents-CF2-CFH-CF3R ' may be branched or straight-chain alkyl having 1 to 20, preferably 1 to 15, carbon atoms, for example methyl, ethyl, n-propyl, sec-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, octyl, decyl, dodecyl, 2-ethylhexyl, etc., R ' may also be a cyclohexyl moiety having 3 to 15, preferably 5 to 12, carbon atoms, for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl, R ' may also be C6 and C15Aryl moieties at 6 carbon atoms such as phenyl, tolyl, naphthyl and the like.
4. The alkali metal salt and the polyglycol fluoroether of claims 2 and 3, both of which in their presence have the following properties: if desired, alkali metal salts can be dissolved in a solvent (e.g., an organic solvent) with the aid of a fluoroether of polyethylene glycol to obtain a very reactive anion from the salt and for dissolving alkali metals similar to macrocyclic ethers, often even superior thereto.
5. The polar aprotic solvent of claim 1, wherein the polar aprotic solvent comprises but is not limited to one or a mixture of two or more of the following: acetonitrile, dimethyl sulfoxide, dimethylformamide, ethylene glycol dimethyl ether.
6. The reaction temperature of claim 1, wherein the reaction is between 0 and 130 degrees CelsiusoReaction at the temperature of C, the preferred reaction temperature is 100-120 DEG CoC。
7. The reaction time according to claim 1, wherein the reaction time is from 0.5 to 5 hours, preferably from 1 to 3 hours.
8. The hexafluoropropylene oligomer of claim 1, wherein said oligomer comprises one or both of hexafluoropropylene dimer and/or hexafluoropropylene trimer.
9. The catalyst to solvent mass ratio of claim 1, wherein the procatalyst: auxiliary catalyst: the mass ratio of the polar aprotic solvent is 1:0.1-10:10-50, preferably 1:1-5: 20-40.
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| CN112961315A (en) * | 2021-02-04 | 2021-06-15 | 河北工业大学 | Preparation method of fluorine-containing polyurethane leather waterproof coating |
| CN113880685A (en) * | 2021-11-04 | 2022-01-04 | 厦门大学 | Synthesis method of hexafluoropropylene oligomer |
| CN113912473A (en) * | 2021-11-11 | 2022-01-11 | 浙江巨化汉正新材料有限公司 | Method for preparing hexafluoropropylene trimer by liquid phase method |
| CN114057539A (en) * | 2021-12-08 | 2022-02-18 | 厦门名大科技有限公司 | Preparation method of hexafluoropropylene oligomer |
| CN115193462A (en) * | 2021-04-01 | 2022-10-18 | 中国石油天然气股份有限公司 | Supported alkali metal catalyst and preparation method thereof |
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