CN101020620A - Process of preparing hexafluoropropylene oligomer - Google Patents
Process of preparing hexafluoropropylene oligomer Download PDFInfo
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- CN101020620A CN101020620A CN 200710067489 CN200710067489A CN101020620A CN 101020620 A CN101020620 A CN 101020620A CN 200710067489 CN200710067489 CN 200710067489 CN 200710067489 A CN200710067489 A CN 200710067489A CN 101020620 A CN101020620 A CN 101020620A
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- hexafluoropropylene
- pressure
- oligomer
- oligomerization reaction
- polyethylene glycol
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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 77
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 7
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 150000007530 organic bases Chemical class 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 8
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-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
- 238000010438 heat treatment Methods 0.000 claims description 4
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229940085675 polyethylene glycol 800 Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- -1 perfluoro nonylene Chemical group 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 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 description 37
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 description 16
- 238000011282 treatment Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- GCESKVLWIQXBGA-UHFFFAOYSA-N 1,1,1,2,3,5,5,6,6,7,7,7-dodecafluoro-2,4-bis(trifluoromethyl)hept-3-ene Chemical compound FC(F)(F)C(F)(C(F)(F)F)C(F)=C(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)F GCESKVLWIQXBGA-UHFFFAOYSA-N 0.000 description 2
- YUWXSBNSEVVXFG-UHFFFAOYSA-N 1,1,1,2,4,5,5,5-octafluoro-3-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-4-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(F)=C(C(F)(C(F)(F)F)C(F)(F)F)C(F)(C(F)(F)F)C(F)(F)F YUWXSBNSEVVXFG-UHFFFAOYSA-N 0.000 description 2
- KJIGYKCIAQBHEL-UHFFFAOYSA-N 1,1,1,4,4,5,5,5-octafluoro-3-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)-2-(trifluoromethyl)pent-2-ene Chemical compound FC(F)(F)C(C(F)(F)F)=C(C(F)(F)C(F)(F)F)C(F)(C(F)(F)F)C(F)(F)F KJIGYKCIAQBHEL-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910021570 Manganese(II) fluoride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- GKKCIDNWFBPDBW-UHFFFAOYSA-M potassium cyanate Chemical compound [K]OC#N GKKCIDNWFBPDBW-UHFFFAOYSA-M 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The process of preparing hexafluoropropylene oligomer with hexafluoropropylene as material, alkali metal fluoride as main catalyst, organic base as co-catalyst and polyether as catalytic promoter includes two sections of pressurized oligomerization reaction in non-protonic polar solvent at 10-150 deg.c, with the weight ratio of main catalyst, co-catalyst, catalytic promoter and non-protonic polar solvent being 1 to 0.1-10 to 1-10 to 8-40. The first section of pressurized oligomerization reaction is performed in a pressure container with hexafluoropropylene gas pressure of 0.1-1.5 MPa, and the second section of pressurized oligomerization reaction is performed in inert gas of pressure 0.1-1.5 MPa. The present invention has the beneficial effects of high hexafluoropropylene converting rate, synergistic catalysis, high perfluoro nonylene selectivity, convenient solvent recovery, etc.
Description
(I) technical field
The invention relates to a preparation method of a hexafluoropropylene oligomer, in particular to a preparation method of a hexafluoropropylene oligomer with more than 99% of perfluorononene mass content.
(II) background of the invention
The perfluorononene is an important fluorine-containing organic intermediate obtained by oligomerization of hexafluoropropylene, and can derive a plurality of fluorine-containing surfactants. The surfactant has high activity, high heat-resistant stability, high chemical inertness and water and oil increasing and repelling performance, and can play a unique role in the fields of coating, washing, fire fighting, metal corrosion prevention, pigment, dye, emulsifying and dispersing agent, fiber leather treating agent, electronic industry, petroleum product and the like. For example, perfluoro alkyl ether generated by the reaction of hexafluoropropylene oligomer and phenol can be prepared into sulfonate type fluorine surfactant if reacting with oleum; if reacting with chlorosulfonic acid, sulfonyl chloride group can be introduced on benzene ring, and further reacting to obtain various fluorine surfactants.
The perfluorononene is prepared from hexafluoropropylene through oligomerization reaction, and is perfluoro-2, 4-dimethyl-3-ethyl-2-pentene (T)1) Perfluoro-4-methyl-3-isopropyl-2-pentene (T)2) And perfluoro-2, 4-dimethyl-3-heptene (T)3) A mixture of (a). The synthesis process of the perfluorononene comprises a gas phase method and a liquid phase method.
The gas phase hexafluoropropylene oligomerization process is a solvent-free process, and is generally a continuous process in which a catalyst is placed in a tubular reactor, hexafluoropropylene gas is subjected to oligomerization reaction through a catalyst layer. The Allied company directly uses active carbon as a catalyst to carry out oligomerization reaction at 350-450 ℃, and the single-pass conversion rate of hexafluoropropylene is only about 30%; the perfluorohexene yield was about 70% based on the consumed hexafluoropropylene, but the case of perfluorononene was not described (US 4377717).
Daikin corporation, Japan, using KF or CsF supported on activated carbon or nickel oxide as a catalystThe reaction is carried out at the temperature of more than 200 ℃, the single-pass conversion rate of hexafluoropropylene can reach more than 70 percent, and the mixture of perfluorohexene and perfluorononene is obtained. The activated carbon is taken as a carrier, the conversion rate of hexafluoropropylene is high, the perfluorononene in the product is slightly more, but the product contains a large amount of by-product C9F16(ii) a When nickel oxide is used as a carrier, although the single-pass conversion rate of hexafluoropropylene is slightly low, the product mainly contains perfluorohexene, and the highest conversion rate can be achieved80％(US 4296265)。
The liquid phase hexafluoropropylene oligomerizing process includes dissolving catalyst in non-proton solvent and introducing hexafluoropropylene gas for reaction, and may be intermittent reaction or continuous reaction.
The catalyst used in the hexafluoropropylene oligomerization process by the liquid phase method mainly comprises fluoride, and metal fluoride (US 2918501), fluorine-containing amine (US 4780559), activated carbon (US 4820883) and the like can be used. The solvents used are generally polar aprotic solvents, such as DMF, ethylene glycol dimethyl ether, acetonitrile and mixtures thereof. The liquid-phase oligomerization of hexafluoropropylene usually produces a mixture of perfluorohexene and perfluorononene, the ratio of which depends primarily on the catalyst. R.A. Proco adopts KSCN as a catalyst, the perfluorononene in the oligomer obtained by oligomerization of hexafluoropropylene is 59.6%, and the perfluorohexene is 36.2%; KCN is used as a catalyst, and perfluorononene and perfluorohexene in the oligomer obtained by oligomerization of hexafluoropropylene are 2.0% and 96.0%; KOCN is used as a catalyst, and perfluorononene and perfluorohexene in the oligomer obtained by hexafluoropropylene oligomerization reaction are 67.8% and 30.2% (ZL 93121609.5). It is clear that the choice of catalyst has a significant influence on the isomer composition of the hexafluoropropylene oligomer.
Disclosure of the invention
The invention aims to provide a preparation method of a hexafluoropropylene oligomer with simple reaction conditions and high perfluorononene yield, and the mass content of the perfluorononene in the hexafluoropropylene oligomer prepared by the preparation method is more than 90%.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows:
a process for the preparation of a hexafluoropropylene oligomer, said process comprising the steps of: hexafluoropropylene is used as a raw material, alkali metal fluoride is used as a main catalyst, organic base is used as an auxiliary catalyst, and polyether is used as a catalytic promoter, and the hexafluoropropylene oligomer is obtained by two-stage pressure oligomerization reaction in an aprotic polar solvent at the temperature of 10-150 ℃; the mass ratio of the main catalyst to the cocatalyst to the catalyst promoter to the aprotic polar solvent is as follows: 1: 0.1-10: 1-10: 8-40, the first stage of pressure oligomerization reaction is carried out in a pressure container, the pressure of hexafluoropropylene gas is 0.1-1.5 MPa (the container is vacuumized before hexafluoropropylene gas is introduced), the second stage of pressure oligomerization reaction is carried out in inert gas, and the pressure of the inert gas is 0.1-1.5 MPa.
The method takes hexafluoropropylene as a raw material, a ternary composite catalytic system, namely an alkali metal fluoride compound as a main catalyst, organic base as an auxiliary catalyst and polyether as a catalytic promoter. The organic base catalyst can adjust the alkalinity of the catalytic system, and the addition of the polyether compound can increase the solvent performance of the alkali metal fluoride compound, so as to well play the synergistic catalytic action of the three-way catalytic system and effectively improve the selectivity of the perfluorononene.
The reaction temperature is too low, and the reaction is relatively smooth, but the reaction speed is too slow. Since the oligomerization of the hexafluoropropylene is a strong exothermic reaction, the reaction temperature cannot be too high, otherwise, the reaction heat cannot be removed in time due to the rapid oligomerization, and the temperature fluctuation is severe. The method comprises the steps of reacting in an aprotic polar solvent at 10-150 ℃, and performing two-stage pressurization to obtain a hexafluoropropylene oligomer mixture mainly containing perfluorononene (the mass content of the perfluorononene can reach more than 90%). The key of the two-stage pressurizing process is that the second stage reaction is carried out under the pressure of inert gas, so that the unreacted hexafluoropropylene dissolved in the aprotic polar solvent is completely converted into an oligomer, the hexafluoropropylene conversion rate is effectively improved, and the yield of the perfluorononene is improved.
The method can further comprise a purification step, wherein the purification step comprises the following steps: adding a polymerization inhibitor into the obtained hexafluoropropylene oligomer, and performing rectification separation to obtain a purified hexafluoropropylene oligomer; the polymerization inhibitor is one of the following: hydroquinone, p-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, p-methoxyphenol or phenothiazine. The adding amount of the polymerization inhibitor is 3-10% of the amount of substances of the hexafluoropropylene oligomer.
Because perfluorononene and perfluorohexene both have unsaturated bonds, a certain amount of polymerization is generated due to the influence of high temperature for a long time in the rectification separation process. The invention can reduce the loss of perfluorononene by adding polymerization inhibitor in the distillation separation, and the perfluorononene (T) in the final product1、T2And T3Mixture of three isomers) can reach over 99.5 percent by mass.
The alkali metal fluoride is one or a mixture of two or more of ① KF, ② CsF, ③ NaF and ④ MnF2。
The organic base is one or a mixture of two or more of ① dimethylamine, ② diethylamine, ③ trimethylamine, ④ triethylamine, ⑤ N-methylpiperidine, ⑥ N, N-dimethylaniline, ⑦ pyridine and ⑧ piperidine.
The polyether is one or a mixture of two or more of ① polyethylene glycol 400, ② polyethylene glycol 600, ③ polyethylene glycol 800, ④ polyethylene glycol 1000, ⑤ polyethylene glycol nonylphenyl ether and ⑥ polyethylene glycol octylphenyl ether.
The aprotic polar solvent is one of ① acetonitrile, ② dimethyl sulfoxide and ③ glycol dimethyl ether or a mixture of two or more of the following.
Preferably, the oligomerization reaction is carried out at 10-100 ℃, the pressure of hexafluoropropylene gas in the first stage of pressure oligomerization reaction is 0.2-1.0 MPa, and the pressure of inert gas in the second stage of pressure oligomerization reaction is 0.2-1.0 MPa.
The mass ratio of the main catalyst to the cocatalyst to the catalyst promoter to the aprotic polar solvent is preferably as follows: 1: 0.1-5: 1-5: 10-20.
Specifically, the method comprises the following steps: hexafluoropropylene is used as a raw material, KF is used as a main catalyst, N-dimethylaniline is used as a cocatalyst, and polyethylene glycol 600 is used as a catalyst promoter, and hexafluoropropylene oligomer is obtained by two-stage pressure oligomerization reaction in dimethyl sulfoxide; the mass ratio of KF, N-dimethylaniline, polyethylene glycol 600 and dimethyl sulfoxide is as follows: 1: 0.1-5: 1-5: 10-20, the first stage of pressure oligomerization reaction is carried out in a pressure container at the temperature of 50-80 ℃ for 1-2 hours under the pressure of hexafluoropropylene gas of 0.5-0.8 MPa, the second stage of pressure oligomerization reaction is carried out in nitrogen for 0.5-1 hour under the temperature of 50-80 ℃, and the pressure of the nitrogen is 0.5-0.8 MPa; and after the reaction is finished, standing for layering, separating a lower-layer liquid product, adding a small amount of zeolite and hydroquinone, wherein the addition amount of the hydroquinone is about 5% of the amount of the hexafluoropropylene oligomer, slowly heating, rectifying and separating, and collecting a 105-110 ℃ fraction product to obtain the purified hexafluoropropylene oligomer.
The invention has the following beneficial effects: the method has the advantages of high hexafluoropropylene conversion rate, synergistic catalysis of three components, good perfluorononene selectivity, convenient solvent recovery, direct application of the recovered solvent without purification, simple operation, high resource utilization rate and less three wastes.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
40mL of dimethyl sulfoxide is measured and put into an autoclave, 2.5g of KF, 2.5g of N, N-dimethylaniline and 2.5g of polyethylene glycol 600 are added respectively, after the autoclave is covered and sealed, the autoclave is connected with a vacuum extractor, air in the vacuum extractor is removed, nitrogen is introduced, the vacuum extractor is vacuumized again, the pressure in the autoclave is zero, and the air exchange operation is carried out for three times. Then introducing hexafluoropropylene gas to make the pressure reach 0.6MPa, opening the stirrer, rotating at 400 rpm, heating to 70 ℃, keeping the pressure and the temperature basically unchanged, and closing a hexafluoropropylene inlet valve after 90 minutes. Stirring to normal pressure, introducing nitrogen to 0.6MPa, reacting at 70 deg.C for 30min, stopping stirring, and cooling. Then the reaction product is transferred to a 1L pear-shaped separating funnel and stands overnight, and after separation, a lower layer of light yellow fluorocarbon is obtained and washed and dried. Through gas chromatographic analysis, the mass content of the perfluorohexene is 2.2 percent, and the mass content of the perfluorononene is 92.8 percent.
Filling about 300mL of oligomerization reaction product into a 500mL four-neck flask, adding a little zeolite and 5g of hydroquinone, slowly heating to a certain temperature, boiling the liquid in the four-neck flask, separating by a rectifying column, controlling a proper reflux ratio, and collecting 105-110 ℃ fraction to obtain a final product, wherein the perfluorononene [ perfluoro-2, 4-dimethyl-3-ethyl-2-pentene (T-2, 4-dimethyl-3-ethyl-2-pentene)1) Perfluoro-4-methyl-3-isopropyl-2-pentene (T)2) And perfluoro-2, 4-dimethyl-3-heptene (T)3) Mixture of]The mass content is 99.5%.
Example 2:
the three-way catalyst was changed to 2.0g KF, 2.0g diethylamine and 2.0g polyethylene glycol nonylphenyl ether, and the other reactions and post-treatments were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 1.4%, the mass content of perfluorononene is 93.2%, and the mass content of perfluorononene after rectification treatment is 99.5%.
Example 3:
the three-way catalyst was changed to 1.5g KF, 2.0g triethylamine and 2.5g polyethylene glycol nonylphenyl ether, the reaction temperature was changed to 150 ℃ and other reaction conditions and post-treatment were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 1.1%, the mass content of perfluorononene is 93.2%, and the mass content of perfluorononene after rectification treatment is 99.6%.
Example 4:
the solvent was changed to 50mL acetonitrile, the three-way catalyst was changed to 2.0g NaF, 2.0g triethylamine and 2.0g polyethylene glycol nonylphenyl ether, the reaction temperature was changed to 50 ℃, the reaction pressure was changed to 1.5MPa, the reaction time was changed to 30min, the polymerization inhibitor was changed to phenothiazine 10g, and the other reaction conditions and the post-treatment were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 3.6%, the mass content of perfluorononene is 91.2%, and the mass content of perfluorononene after rectification treatment is 99.5%.
Example 5:
the solvent was changed to 50mL acetonitrile, the three-way catalyst was changed to 1.5g CsF, 5.5g N-methylpiperidine and 5.0g polyethylene glycol octylphenyl ether, the reaction temperature was changed to 50 ℃ and other reaction conditions and workup were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 3.1%, the mass content of perfluorononene is 95.3%, and the mass content of perfluorononene after rectification treatment is 99.8%.
Example 6:
the reaction temperature was changed to 80 ℃ and the first-stage reaction pressure was changed to 0.1MPa, the reaction time was 8 hours, the polymerization inhibitor was changed to p-methoxyphenol 9g, and the other reaction conditions and the post-treatment were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 2.3%, the mass content of perfluorononene is 91.9%, and the mass content of perfluorononene after rectification treatment is 99.7%.
Example 7:
the reaction temperature was changed to 30 ℃ and the first-stage reaction pressure was changed to 1.0MPa, the reaction time was 10 hours, the polymerization inhibitor was changed to 10g of 2, 6-di-t-butyl-p-cresol, and the other reaction conditions and the post-treatment were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 2.0 percent, the mass content of perfluorononene is 92.7 percent, and the mass content of perfluorononene after rectification treatment is 99.5 percent.
Example 8:
the three-way catalyst was changed to 1.5g of CsF, 5.5g N-methylpiperidine and 5.0g of polyethylene glycol octylphenyl ether, the reaction temperature was changed to 50 deg.C, the first-stage reaction pressure was changed to 0.5MPa, the reaction time was 2 hours, the polymerization inhibitor was changed to 18g of p-tert-butylphenol, and the other reaction conditions and post-treatment were the same as in example 1. The mass content of perfluorohexene in the hexafluoropropylene oligomerization product is 1.0%, the mass content of perfluorononene is 93.7%, and the mass content of perfluorononene after rectification treatment is 99.5%.
Claims (10)
1. A process for the preparation of a hexafluoropropylene oligomer, said process comprising the steps of: hexafluoropropylene is used as a raw material, alkali metal fluoride is used as a main catalyst, organic base is used as an auxiliary catalyst, and polyether is used as a catalytic promoter, and the hexafluoropropylene oligomer is obtained by two-stage pressure oligomerization reaction in an aprotic polar solvent at the temperature of 10-150 ℃; the mass ratio of the main catalyst to the cocatalyst to the catalyst promoter to the aprotic polar solvent is as follows: 1: 0.1-10: 1-10: 8-40, the first stage of pressure oligomerization reaction is carried out in a pressure container under the pressure of hexafluoropropylene gas of 0.1-1.5 MPa, and the second stage of pressure oligomerization reaction is carried out in inert gas of 0.1-1.5 MPa.
2. The process forthe preparation of hexafluoropropylene oligomer as set forth in claim 1, wherein said process further comprises the step of purifying: adding a polymerization inhibitor into the obtained hexafluoropropylene oligomer, and performing rectification separation to obtain a purified hexafluoropropylene oligomer; the polymerization inhibitor is one of the following: hydroquinone, p-tert-butylphenol, 2, 6-di-tert-butyl-p-cresol, p-methoxyphenol or phenothiazine.
3. A process for the preparation of hexafluoropropylene oligomers as claimed in claim 1 or 2, wherein: the addition amount of the polymerization inhibitor is as follows: the amount of hexafluoropropylene oligomer is 3-10%.
4. A process for producing a hexafluoropropylene oligomer as claimed in claim 1 or 2, wherein said alkali metal fluoride is one of ① KF, ② CsF, ③ NaF, ④ MnF or a mixture of two or more thereof2。
5. The process for producing a hexafluoropropylene oligomer according to claim 1 or 2, wherein the organic base is one of ① dimethylamine, ② diethylamine, ③ trimethylamine, ④ triethylamine, ⑤ N-methylpiperidine, ⑥ N, N-dimethylaniline, ⑦ pyridine, ⑧ piperidine or a mixture of two or more thereof.
6. The process for producing a hexafluoropropylene oligomer according to claim 1 or 2, wherein the polyether is one of ① polyethylene glycol 400, ② polyethylene glycol 600, ③ polyethylene glycol 800, ④ polyethylene glycol 1000, ⑤ polyethylene glycol nonylphenyl ether, ⑥ polyethylene glycol octylphenyl ether, or a mixture of two or more thereof.
7. The process for producing a hexafluoropropylene oligomer according to claim 1 or 2, wherein the aprotic polar solvent is one or a mixture of two or more of ① acetonitrile, ② dimethyl sulfoxide and ③ ethylene glycol dimethyl ether.
8. The process for producing a hexafluoropropylene oligomer according to claim 1 or 2, wherein the oligomerization reaction is carried out at 10 to 100 ℃, the hexafluoropropylene gas pressure is 0.2 to 1.0MPa in the first stage of the pressure oligomerization reaction, and the second stage of the pressure oligomerization reaction is carried out in an inert gas pressure of 0.2 to 1.0 MPa.
9. The process for preparing hexafluoropropylene oligomer according to claim 1 or 2, wherein the mass ratio of the main catalyst, the cocatalyst, the catalyst promoter and the aprotic polar solvent is: 1: 0.1-5: 1-5: 10-20.
10. A process for the preparation of hexafluoropropylene oligomers as claimed in claim 1, characterized in that said process comprises: hexafluoropropylene is used as a raw material, KF is used as a main catalyst, N-dimethylaniline is used as a cocatalyst, and polyethylene glycol 600 is used as a catalyst promoter, and hexafluoropropylene oligomer is obtained by two-stage pressure oligomerization reaction in dimethyl sulfoxide; the mass ratio of KF, N-dimethylaniline, polyethylene glycol 600 and dimethyl sulfoxide is as follows: 1: 0.1-5: 1-5: 10-20, carrying out a first stage of pressure oligomerization reaction in a vacuum container at the pressure of 0.5-0.8 MPa and the temperature of 50-80 ℃ for 1-2 hours, and carrying out a second stage of pressure oligomerization reaction in nitrogen at the temperature of 50-80 ℃ for 0.5-1 hour, wherein the pressure of the nitrogen is 0.5-0.8 MPa; and after the reaction is finished, standing for layering, separating, taking a lower-layer liquid product, adding zeolite and hydroquinone, slowly heating, performing rectification separation, and collecting a fraction product at 105-110 ℃ to obtain the purified hexafluoropropylene oligomer, wherein the addition amount of the hydroquinone is about 5% of the amount of the hexafluoropropylene oligomer.
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| CN101759522A (en) * | 2008-11-14 | 2010-06-30 | 王凤娇 | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene |
| CN103752342A (en) * | 2014-01-06 | 2014-04-30 | 巨化集团技术中心 | Preparation method of catalyst for synthesizing hexafluoropropene tripolymer |
| CN110841677A (en) * | 2019-12-09 | 2020-02-28 | 朱润栋 | Preparation and application method of hexafluoropropylene dimer isomerization catalyst |
| CN111269081A (en) * | 2020-03-12 | 2020-06-12 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3917724A (en) * | 1973-02-09 | 1975-11-04 | Hoechst Ag | Process for preparing oligomers of hexafluoropropene |
| JPS51125307A (en) * | 1975-04-17 | 1976-11-01 | Central Glass Co Ltd | Process for preparation of hexafluoropropene oligomers |
| CN1030406A (en) * | 1987-06-29 | 1989-01-18 | 上海市有机氟材料研究所 | Make the method for the oligomerization of hexafluoropropylene that contains freonll-11 |
| US5254774A (en) * | 1992-12-28 | 1993-10-19 | Minnesota Mining And Manufacturing Company | Preparation of hexafluoropropene oligomers |
| CN1876611A (en) * | 2006-02-27 | 2006-12-13 | 浙江莹光化工有限公司 | Hexafluoropropylene dimmer production method |
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| CN101759522A (en) * | 2008-11-14 | 2010-06-30 | 王凤娇 | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene |
| CN103752342A (en) * | 2014-01-06 | 2014-04-30 | 巨化集团技术中心 | Preparation method of catalyst for synthesizing hexafluoropropene tripolymer |
| CN103752342B (en) * | 2014-01-06 | 2015-07-15 | 巨化集团技术中心 | Preparation method of catalyst for synthesizing hexafluoropropene tripolymer |
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| TWI768009B (en) * | 2017-03-21 | 2022-06-21 | 美商3M新設資產公司 | Heat transfer fluids and methods of using same |
| CN110841677A (en) * | 2019-12-09 | 2020-02-28 | 朱润栋 | Preparation and application method of hexafluoropropylene dimer isomerization catalyst |
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| CN113548937A (en) * | 2020-04-26 | 2021-10-26 | 浙江蓝天环保高科技股份有限公司 | Continuous preparation method of high-purity perfluoro-2, 4-dimethyl-3-heptene |
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