CN100537500C - Process of preparing hexafluoropropylene oligomer - Google Patents
Process of preparing hexafluoropropylene oligomer Download PDFInfo
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- CN100537500C CN100537500C CNB2007100674894A CN200710067489A CN100537500C CN 100537500 C CN100537500 C CN 100537500C CN B2007100674894 A CNB2007100674894 A CN B2007100674894A CN 200710067489 A CN200710067489 A CN 200710067489A CN 100537500 C CN100537500 C CN 100537500C
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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 50
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- -1 perfluoro nonylene Chemical group 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 150000007530 organic bases Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 58
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 8
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 6
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 5
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229940057847 polyethylene glycol 600 Drugs 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 229920004890 Triton X-100 Polymers 0.000 claims description 4
- 239000013504 Triton X-100 Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 239000000126 substance Substances 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 239000007788 liquid Substances 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
- 239000010457 zeolite Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006384 oligomerization reaction Methods 0.000 abstract description 20
- 239000007789 gas Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000011261 inert gas Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical class CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 38
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000002153 concerted effect Effects 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
- 239000000376 reactant Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye 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
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 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
- 238000006116 polymerization reaction Methods 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
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- 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
(1) technical field
The present invention relates to a kind of preparation method of hexafluoropropene oligomers, the preparation method of the hexafluoropropene oligomers of especially a kind of perfluorinated nonene mass content more than 99%.
(2) background technology
Perfluorinated nonene is the important fluorine-containing organic intermediate that is obtained by oligomerization of hexafluoropropene, can derive many fluorochemical surfactants.This class tensio-active agent has high reactivity, high heat-resistant stability, high unreactiveness and the oil repellency energy of surging, and makes it can bring into play unique effect in fields such as coating, washing, fire-fighting, anti-corrosion of metal, pigment, dyestuff, emulsifying dispersant, fiber leather treatment, electronic industry, petroleum products.For example the perfluoroalkyl ether of the oligopolymer of R 1216 and phenol reactant generation if react with oleum, can be made into the sulfonate type fluorine surfactant; If then can introduce sulfuryl chlorio on phenyl ring with the chlorsulfonic acid reaction, further reaction can be made into various fluorine surfactants.
Perfluorinated nonene is got through oligomerisation reaction by R 1216, and it is a perfluor-2,4-dimethyl-3-ethyl-2-amylene (T
1), perfluor-4-methyl-3-sec.-propyl-2-amylene (T
2) and perfluor-2,4-dimethyl-3-heptene (T
3) mixture.The building-up process of perfluorinated nonene has two kinds of vapor phase process and liquid phase methods.
Vapor phase process oligomerization of hexafluoropropylene technology is solvent-free process, normally catalyzer is placed tubular reactor, allows R 1216 gas by catalyst layer generation oligomerisation reaction, and this technological process is generally successive reaction.Allied company directly uses gac as catalyzer, carries out oligomerisation reaction under 350～450 ℃, and the per pass conversion of R 1216 only is about 30%; Calculate with the R 1216 that consumes, the yield of perfluor hexene is about 70%, but the situation of perfluorinated nonene is not described (US 4377717).
The Daikin company of Japan is a catalyzer with the KF or the CsF that are carried on gac, nickel oxide, is reacting more than 200 ℃, and the R 1216 per pass conversion can reach more than 70%, obtains the mixture of perfluor hexene and perfluorinated nonene.With the gac is carrier, and the transformation efficiency of R 1216 is higher, and perfluorinated nonene is slightly many in the product, but contains a large amount of by product C in the product
9F
16When being carrier with the nickel oxide, though the R 1216 per pass conversion is lower slightly, product reaches as high as 80% (US 4296265) based on the perfluor hexene.
Liquid phase method oligomerization of hexafluoropropylene technology is that catalyzer is dissolved in the aprotic solvent, feeds R 1216 gas then and reacts, and its technology can be rhythmic reaction, also can be successive reaction.
The used catalyzer of liquid phase method oligomerization of hexafluoropropylene technology can use metal fluoride (US 2918501), fluorine-containing amine (US 4780559) and gac (US 4820883) etc. mainly based on fluorochemical.The solvent that uses is generally polar aprotic solvent, for example DMF, glycol dimethyl ether, acetonitrile and their mixture.R 1216 liquid phase oligomerisation reaction obtains the mixture of perfluor hexene and perfluorinated nonene usually, and the ratio of perfluor hexene and perfluorinated nonene depends primarily on catalyzer.R.A. Liese Prokop employing KSCN is a catalyzer, and perfluorinated nonene is 59.6% in the oligopolymer that oligomerization of hexafluoropropylene obtains, and the perfluor hexene is 36.2%; With KCN is catalyzer, and perfluorinated nonene is 2.0% in the oligopolymer that oligomerization of hexafluoropropylene obtains, and the perfluor hexene is 96.0%; With KOCN is catalyzer, and perfluorinated nonene is 67.8% in the oligopolymer that oligomerization of hexafluoropropene obtains, and the perfluor hexene is 30.2% (ZL93121609.5).Obviously selection of catalysts is formed the isomer of oligomerization of hexafluoropropylene body significant effects.
(3) summary of the invention
The object of the invention is to provide the preparation method of the hexafluoropropene oligomers that a kind of reaction conditions is simple, the perfluorinated nonene yield is high, makes that the perfluorinated nonene mass content reaches more than 90% in the hexafluoropropene oligomers.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of preparation method of hexafluoropropene oligomers, described method comprises the steps: with the R 1216 to be raw material, with the alkaline metal fluoride cpd is that Primary Catalysts, organic bases are that promotor, polyethers are catalytic promoter, in aprotic polar solvent, under 10～150 ℃, through two sections pressurization oligomerisation reactions, obtain described hexafluoropropene oligomers; Described Primary Catalysts, promotor, catalyst promoting agent, aprotic polar solvent mass ratio are: 1:0.1～10:1～10:8～40, first section pressurization oligomerisation reaction is in pressurized vessel, carry out under R 1216 gaseous tension 0.1～1.5MPa (container vacuumized earlier before feeding R 1216 gas), second section pressurization oligomerisation reaction carries out in rare gas element, and inert gas pressure is 0.1～1.5MPa.
The inventive method is raw material with the R 1216, is that the alkali metal fluosilicate compound is that Primary Catalysts, organic bases are promotor with the ternary composite catalyst system, and polyethers is a catalytic promoter.Organic alkali catalyst can be regulated the alkalescence of catalyst system, adds polyether compound, can increase the solvent nature of alkali metal fluosilicate compound, to bring into play the concerted catalysis effect of three-element catalytic system well, effectively improves the selectivity of perfluorinated nonene.
Reaction temperature is spent low, though reaction is more steady, speed of response is too slow.Because oligomerization of hexafluoropropylene is stronger thermopositive reaction, temperature of reaction can not be too high, otherwise carry out fast because of oligomerisation, and reaction heat can't in time be removed, and can cause temperature fluctuation violent.The present invention in 10～150 ℃ of reactions, through two sections pressure processes, obtains the oligomerization of hexafluoropropylene body mixture (the perfluorinated nonene mass content can reach more than 90%) based on perfluorinated nonene in aprotic polar solvent.The key of two sections pressure processes is that second section reaction is to carry out under inert gas pressure, purpose is to improve the unreacted R 1216 total overall reaction that is dissolved in the aprotic polar solvent to be converted into oligomer, effectively improve the R 1216 transformation efficiency, improve the yield of perfluorinated nonene.
Described method also can comprise purification step, and described purification step is: with the gained hexafluoropropene oligomers, add stopper and carry out rectifying separation, obtain the hexafluoropropene oligomers behind the purifying; Described stopper is one of following: Resorcinol, p-tert-butylphenol, 2,6 ditertiary butyl p cresol, p methoxy phenol or thiodiphenylamine.3～10% of the amount of substance that described stopper add-on is a hexafluoropropene oligomers.
Because perfluorinated nonene and perfluor hexene all have unsaturated link(age), in the rectifying separation process, because long-time temperatures involved produces a certain amount of polymerization.Rectifying separation of the present invention is added stopper, can reduce the loss of perfluorinated nonene, perfluorinated nonene (T in the final product
1, T
2And T
3Three kinds of mixture of isomers) mass content can reach more than 99.5%.
Described alkaline metal fluoride cpd is one of following or two or more mixture wherein: 1. KF, 2. CsF, 3. NaF, 4. MnF
2
Described organic bases is one of following or two or more mixture wherein: 1. dimethylamine, 2. diethylamine, 3. Trimethylamine 99,4. triethylamine, 5. N-methyl piperidine, 6. N, N-xylidene(s), 7. pyridine, 8. piperidines.
Described polyethers is one of following or two or more mixture wherein: 1. poly(oxyethylene glycol) 400,2. Polyethylene Glycol-600,3. polyoxyethylene glycol 800,4. cetomacrogol 1000,5. polyethylene glycol nonylphenyl ether, 6. Triton X-100.
Described aprotic polar solvent is one of following or two or more mixture wherein: 1. acetonitrile, 2. dimethyl sulfoxide (DMSO), 3. glycol dimethyl ether.
Preferably, described oligomerisation reaction carries out under 10～100 ℃, and in first section pressurization oligomerisation reaction, the R 1216 gaseous tension is 0.2～1.0MPa, and second section pressurization oligomerisation reaction carries out in rare gas element, and inert gas pressure is 0.2～1.0MPa.
Described Primary Catalysts, promotor, catalyst promoting agent, aprotic polar solvent mass ratio are preferably: 1:0.1～5:1～5:10～20.
Concrete, described method is as follows: with the R 1216 is raw material, is Primary Catalysts, N with KF, the N-xylidene(s) is that promotor, Polyethylene Glycol-600 are catalytic promoter, in dimethyl sulfoxide (DMSO), through two sections pressurization oligomerisation reactions, obtains hexafluoropropene oligomers; Described KF, N, N-xylidene(s), Polyethylene Glycol-600, dimethyl sulfoxide (DMSO) mass ratio are: 1:0.1～5:1～5:10～20, first section pressurization oligomerisation reaction is in pressurized vessel, carried out 1～2 hour under the R 1216 gaseous tension 0.5～0.8MPa, 50～80 ℃, second section pressurization oligomerisation reaction carried out 0.5～1 hour in nitrogen, under 50～80 ℃, and nitrogen pressure is 0.5～0.8MPa; After reaction finishes, standing demix, separation is taken off a layer product liquid and is added a little zeolite and Resorcinol, the Resorcinol add-on be hexafluoropropene oligomers amount of substance about 5%, slowly heating, rectifying separation is collected 105～110 ℃ of cut products, promptly gets the hexafluoropropene oligomers behind the purifying.
Beneficial effect of the present invention is mainly reflected in: R 1216 transformation efficiency height, ternary component concerted catalysis, good, the convenient solvent reclaiming of perfluorinated nonene selectivity, and recovered solvent can directly be applied mechanically without purifying, and is simple to operate, the resource utilization height, the three wastes are few.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Measure the 40mL dimethyl sulfoxide (DMSO) and put into autoclave, add 2.5g KF more respectively, 2.5gN, N-xylidene(s) and 2.5g Polyethylene Glycol-600, after building sealing, connect vacuum extractor, remove air wherein, feed nitrogen, vacuumize, making the still internal pressure is zero again, the operation three times of taking a breath.Feed R 1216 gas then, make pressure reach 0.6MPa, open agitator, 400 rev/mins, be heated to 70 ℃, it is constant substantially with temperature to keep-up pressure, and after 90 minutes, closes the R 1216 inlet valve.Continue to be stirred to normal pressure, feed nitrogen to 0.6MPa, 70 ℃ were reacted 30 minutes, stopped to stir cooling.Then reactant transfer to the 1L pear shape separatory funnel, standing over night obtains the faint yellow fluorocarbon of lower floor, washing and drying after the separation.Through gas chromatographic analysis, wherein perfluor hexene mass content 2.2%, perfluorinated nonene mass content 92.8%.
In the 500mL four-hole boiling flask, pack into oligomerisation reaction product about about 300mL, and add a little zeolite and 5g Resorcinol, slowly be heated to certain temperature, liquid boiling in the four-hole boiling flask, separate through rectifying column, control suitable reflux ratio, collect 105～110 ℃ of cuts and get final product, perfluorinated nonene [perfluor-2,4-dimethyl-3-ethyl-2-amylene (T wherein
1), perfluor-4-methyl-3-sec.-propyl-2-amylene (T
2) and perfluor-2,4-dimethyl-3-heptene (T
3) mixture] mass content is 99.5%.
Embodiment 2:
Three-way catalyst changes 2.0g KF into, 2.0g diethylamine and 2.0g polyethylene glycol nonylphenyl ether, and other reaction is identical with example 1 with aftertreatment.Perfluor hexene mass content 1.4%, perfluorinated nonene mass content 93.2% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.5% after the rectification process.
Embodiment 3:
Three-way catalyst changes 1.5g KF into, 2.0g triethylamine and 2.5g polyethylene glycol nonylphenyl ether, and temperature of reaction changes 150 ℃ into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 1.1%, perfluorinated nonene mass content 93.2% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.6% after the rectification process.
Embodiment 4:
Solvent changes the 50mL acetonitrile into, three-way catalyst changes 2.0g NaF into, 2.0g triethylamine and 2.0g polyethylene glycol nonylphenyl ether, temperature of reaction changes 50 ℃ into, reaction pressure changes 1.5MPa into, reaction times changes 30min into, and stopper changes thiodiphenylamine 10g into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 3.6%, perfluorinated nonene mass content 91.2% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.5% after the rectification process.
Embodiment 5:
Solvent changes the 50mL acetonitrile into, and three-way catalyst changes 1.5g CsF into, 5.5g N-methyl piperidine and 5.0g Triton X-100, and temperature of reaction changes 50 ℃ into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 3.1%, perfluorinated nonene mass content 95.3% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.8% after the rectification process.
Embodiment 6:
Temperature of reaction changes 80 ℃ into, and first section reaction pressure changes 0.1MPa into, and in 8 hours reaction times, stopper changes p methoxy phenol 9g into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 2.3%, perfluorinated nonene mass content 91.9% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.7% after the rectification process.
Embodiment 7:
Temperature of reaction changes 30 ℃ into, and first section reaction pressure changes 1.0MPa into, and in 10 hours reaction times, stopper changes 2,6 ditertiary butyl p cresol 10g into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 2.0%, perfluorinated nonene mass content 92.7% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.5% after the rectification process.
Embodiment 8:
Three-way catalyst changes 1.5g CsF into, 5.5gN-methyl piperidine and 5.0g Triton X-100, and temperature of reaction changes 50 ℃ into, first section reaction pressure changes 0.5MPa into, in 2 hours reaction times, stopper changes the 18g p-tert-butylphenol into, and other reaction conditions is identical with example 1 with aftertreatment.Perfluor hexene mass content 1.0%, perfluorinated nonene mass content 93.7% in the oligomerization of hexafluoropropylene product, the perfluorinated nonene mass content is 99.5% after the rectification process.
Claims (8)
1. the preparation method of a hexafluoropropene oligomers, described method comprises the steps: with the R 1216 to be raw material, with the alkaline metal fluoride cpd is that Primary Catalysts, organic bases are that promotor, polyethers are catalytic promoter, in aprotic polar solvent, under 10～150 ℃, through two sections pressurization oligomerisation reactions, obtain described hexafluoropropene oligomers; Described Primary Catalysts, promotor, catalyst promoting agent, aprotic polar solvent mass ratio are: 1:0.1～10:1～10:8～40, first section pressurization oligomerisation reaction is in pressurized vessel, carry out under R 1216 gaseous tension 0.1～1.5MPa, second section pressurization oligomerisation reaction carries out in nitrogen, and nitrogen pressure is 0.1～1.5MPa; Described organic bases is one of following or two or more mixture wherein: 1. dimethylamine, 2. diethylamine, 3. Trimethylamine 99,4. triethylamine, 5. N-methyl piperidine, 6. N, N-xylidene(s), 7. pyridine, 8. piperidines; Described aprotic polar solvent is one of following or two or more mixture wherein: 1. acetonitrile, 2. dimethyl sulfoxide (DMSO), 3. glycol dimethyl ether.
2. the preparation method of hexafluoropropene oligomers as claimed in claim 1, it is characterized in that described method also comprises purification step, described purification step is: with the gained hexafluoropropene oligomers, add stopper and carry out rectifying separation, obtain the hexafluoropropene oligomers behind the purifying; Described stopper is one of following: Resorcinol, p-tert-butylphenol, 2,6 ditertiary butyl p cresol, p methoxy phenol or thiodiphenylamine.
3. the preparation method of hexafluoropropene oligomers as claimed in claim 2, it is characterized in that: described stopper add-on is: 3～10% of the amount of substance of hexafluoropropene oligomers.
4. the preparation method of hexafluoropropene oligomers as claimed in claim 1 or 2 is characterized in that described alkaline metal fluoride cpd is one of following or two or more mixture wherein: 1. KF, 2. CsF, 3. NaF.
5. the preparation method of hexafluoropropene oligomers as claimed in claim 1 or 2 is characterized in that described polyethers is one of following or two or more mixture wherein: 1. poly(oxyethylene glycol) 400,2. Polyethylene Glycol-600,3. polyoxyethylene glycol 800,4. cetomacrogol 1000,5. polyethylene glycol nonylphenyl ether, 6. Triton X-100.
6. the preparation method of hexafluoropropene oligomers as claimed in claim 1 or 2, it is characterized in that described oligomerisation reaction carries out under 10～100 ℃, in first section pressurization oligomerisation reaction, the R 1216 gaseous tension is 0.2～1.0MPa, second section pressurization oligomerisation reaction carries out in nitrogen, and nitrogen pressure is 0.2～1.0MPa.
7. the preparation method of hexafluoropropene oligomers as claimed in claim 1 or 2 is characterized in that described Primary Catalysts, promotor, catalyst promoting agent, aprotic polar solvent mass ratio are: 1:0.1～5:1～5:10～20.
8. the preparation method of hexafluoropropene oligomers as claimed in claim 1, it is characterized in that described method is as follows: be raw material with the R 1216, with KF is Primary Catalysts, N, the N-xylidene(s) is that promotor, Polyethylene Glycol-600 are catalytic promoter, in dimethyl sulfoxide (DMSO), through two sections pressurization oligomerisation reactions, obtain hexafluoropropene oligomers; Described KF, N, N-xylidene(s), Polyethylene Glycol-600, dimethyl sulfoxide (DMSO) mass ratio are: 1:0.1～5:1～5:10～20, first section pressurization oligomerisation reaction is in vacuum vessel, carried out 1～2 hour under the R 1216 gaseous tension 0.5～0.8MPa, 50～80 ℃, second section pressurization oligomerisation reaction carried out 0.5～1 hour in nitrogen, under 50～80 ℃, and nitrogen pressure is 0.5～0.8MPa; After reaction finished, standing demix separated and takes off layer a product liquid adding zeolite and a Resorcinol, the Resorcinol add-on be about hexafluoropropene oligomers amount of substance 5%, slowly heating, rectifying separation, collect 105～110 ℃ of cut products, promptly get the hexafluoropropene oligomers behind the purifying.
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| CN101759522A (en) * | 2008-11-14 | 2010-06-30 | 王凤娇 | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene |
| CN103752342B (en) * | 2014-01-06 | 2015-07-15 | 巨化集团技术中心 | Preparation method of catalyst for synthesizing hexafluoropropene tripolymer |
| CN109072054B (en) * | 2017-03-21 | 2021-10-19 | 3M创新有限公司 | Heat transfer fluid and method of use |
| CN110841677A (en) * | 2019-12-09 | 2020-02-28 | 朱润栋 | Preparation and application method of hexafluoropropylene dimer isomerization catalyst |
| CN111269081B (en) * | 2020-03-12 | 2022-08-09 | 浙江巨化汉正新材料有限公司 | Preparation method of hexafluoropropylene tripolymer |
| CN113548937B (en) * | 2020-04-26 | 2023-09-05 | 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 |
| CN111606778A (en) * | 2020-06-29 | 2020-09-01 | 厦门名大科技有限公司 | Catalytic synthesis method of hexafluoropropylene oligomer |
| CN113880685B (en) * | 2021-11-04 | 2023-04-25 | 厦门大学 | Synthesis method of hexafluoropropylene oligomer |
| CN116273164A (en) * | 2023-03-16 | 2023-06-23 | 浙江锦华新材料股份有限公司 | Isomerization reaction catalyst of perfluoro-4-methyl-2-pentene |
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| US4042638A (en) * | 1975-04-17 | 1977-08-16 | Central Glass Co., Ltd. | Process for preparing oligomers of hexafluoropropene |
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