CN105061162A - Preparation method of 1, 1, 2, 2,-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether - Google Patents
Preparation method of 1, 1, 2, 2,-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether Download PDFInfo
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- CN105061162A CN105061162A CN201510458942.9A CN201510458942A CN105061162A CN 105061162 A CN105061162 A CN 105061162A CN 201510458942 A CN201510458942 A CN 201510458942A CN 105061162 A CN105061162 A CN 105061162A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 24
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- HLFWEZRGOIEVLU-UHFFFAOYSA-N 1,1,1-trifluorobutan-2-yl hypofluorite Chemical class C(C)C(C(F)(F)F)OF HLFWEZRGOIEVLU-UHFFFAOYSA-N 0.000 claims description 19
- -1 octyl sulfuryl amine Chemical class 0.000 claims description 15
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract 1
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 1
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- HDBGBTNNPRCVND-UHFFFAOYSA-N 3,3,3-trifluoropropan-1-ol Chemical compound OCCC(F)(F)F HDBGBTNNPRCVND-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WZCZNEGTXVXAAS-UHFFFAOYSA-N trifluoromethanol Chemical compound OC(F)(F)F WZCZNEGTXVXAAS-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
- B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of 1, 1, 2, 2,-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether. The method comprises the steps of: (a) by weight, reacting 100 parts of strongly basic anion exchange resin, 200-400 parts of water, 0.1-0.5 part of N-hydroxyethyl perfluorooctane sulfonamide, 5-20 parts of 1, 8-diazabicyclo (5, 4, 0)undec-7-ene, and 0.05-0.5 part of ethylenediamine tetraacetic acid disodium at 40DEG C-80DEG C for 10-20h to obtain a composite catalyst for standby use; and (b) by weight, adding 100 parts of trifluoroethanol and 30-100 parts of the composite catalyst prepared in step (1) into a reaction kettle, then introducing a tetrafluoroethylene monomer to carry out reaction at 40-80DEG C, after introduction of 300-500 parts of the tetrafluoroethylene monomer, ending the reaction, performing filtering and recovering the composite catalyst, and subjecting the filtrate to washing and refining, thus obtaining 1, 1, 2, 2,-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether. The 1, 1, 2, 2,-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether prepared by the method provided by the invention has the advantages of good activity, recyclability, few three wastes, green and environmental protection.
Description
Technical field
The present invention relates to the preparation method of fluorine-containing ether compounds, particularly a kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers.
Background technology
It is CF that Daikin and Asahi Glass are all proposed molecular formula
3cH
20CF
2cHF
2hydrogen fluorine ether, the commercialization name of great Jin is called HFE-S7, and the commercialization name of Asahi Glass is called AE3000, is called AE3100 (having another name called HFE347pc-f) by commercialization name after alcohol dilution.The numerous characteristics of HFE-347pc-f and CFC-113 are relatively, without the need to large adjustment in using method, but because its KB value is less than CFC-113, solvency power is slightly poor, so have difference again during use, the KB value of HFE-347pc-f is less, solvency power is more weak, so need during cleaning to use ultrasonic assistant.Simultaneously, suitable KB value makes it can have good consistency with most of material, be easy to reclaim and use, the feature of the low latent heat of vaporization makes it to have in same kind solvent evaporation rate faster, be good dry solvent, but also have larger volatilization loss simultaneously, so, cleaning machine with cooling and reflux device will greatly reduce volatilization loss, cost-saving.In addition, because HFE-347pc-f and most of solvent have good mutual solubility, can use with the solvent of solvency power strong (KB value is larger), learning from other's strong points to offset one's weaknesses, is a kind of excellent clean-out system.
China Patent Publication No. CN1651378A provides a kind of new hydrofluoro ether and preparation method thereof, in dimethyl formamide DMF or dimethyl sulfoxide (DMSO) DMSO organic solvent, potassium hydroxide or sodium hydroxide is used to be catalyzer, prepare new hydrofluoro ether, raw material is trifluoro-ethylene, tetrafluoroethylene, vinylidene, R 1216, trifluorochloroethylene and trifluoroethanol, trifluoropropanol, methyl alcohol, ethanol, propyl alcohol, butanols, at 20 ~ 90 DEG C of reaction 1 ~ 10h, obtained hydrogen fluorine ether.
China Patent Publication No. CN102115428A provides a kind of synthetic method of hydrogen fluorine ether, according to ratio of weight and number with 20 ~ 100 parts of alcohol for raw material, described alcohols is a kind of in methyl alcohol, ethanol, propyl alcohol, trifluoro methyl alcohol, C3-Fluoroalcohol and octafluoropentanol, under 1 ~ 6 part of alkali catalyst exists, add 34 ~ 108 parts of Fluorine containing olefines continuously, react at 110 ~ 180 DEG C, reaction pressure is 0.6 ~ 1.2MPa, reaction times is 1 ~ 5h, after rectifying separation, obtain target product.
Above patent and catalyzer that technical literature uses are mainly alkali metal compound, and there is catalyst recovery difficulty, dregginess is high, and because solid particulate is thin, the shortcomings such as product and catalyst separating difficulty, simultaneously because use a large amount of solvent, easily cause environmental pollution.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, and provide a kind of good catalyst activity, product is easily separated, the preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers of environmental protection.
In order to solve above technical problem, present invention employs following technical scheme: a kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
A () by weight, by strongly basic anion exchange resin 100 parts, 200 ~ 400 parts, water, N-hydroxyethyl perfluorinated octyl sulfuryl amine 0.1 ~ 0.5 part, 1,8-diazabicyclo (5,4,0) 11 5 ~ 20 parts, carbon-7-alkene, disodium ethylene diamine tetraacetate 0.05 ~ 0.5 part, at 40 DEG C ~ 80 DEG C reaction 10 ~ 20h, obtained composite catalyst, for subsequent use;
B () by weight, 100 parts of trifluoroethanols, composite catalyst that 30 ~ 100 parts of steps (1) are obtained are added reactor, then passes into tetrafluoroethylene monomer and react at 40 ~ 80 DEG C, after passing into 300 ~ 500 parts of tetrafluoroethylene monomers, terminate reaction, filtered and recycled composite catalyst, filtrate obtains 1,1,2 through washing to refine, 2,-four fluoro ethyl-2,2,2-trifluoroethyl ethers.
The described temperature of reaction of step (a) is preferably 50 DEG C ~ 70 DEG C, and the reaction times is preferably 12 ~ 18h.
The described temperature of reaction of step (b) is preferably 50 DEG C ~ 70 DEG C.
Of the present invention 1,1,2,2 ,-four fluoro ethyls-2,2, the preparation method of 2-trifluoroethyl ether carries out in two steps, first prepares solid composite catalyst, then uses tetrafluoroethylene and trifluoroethanol as raw material, under the catalysis of solid composite catalyst, carry out etherification reaction obtain 1,1,2,2,-four fluoro ethyl-2,2,2-trifluoroethyl ether products.When preparing solid composite catalyst, N-hydroxyethyl perfluorinated octyl sulfuryl amine, 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), disodium ethylene diamine tetraacetate (EDTA) is as alkaline enhanced aid, can be adsorbed on resin surface, the comprehensive alkalescence of composite catalyst is strengthened, and catalyst activity is better.Use solid composite catalyst catalysis tetrafluoroethylene and trifluoroethanol to carry out etherification reaction and obtain 1,1,2,2,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, solid composite catalyst and product are easy to be separated, and the composite catalyst reclaimed can recycle, and effectively decreases the discharge of waste residue.The present invention not with an organic solvent, to avoid in prior art volatile organic solvent to the pollution of environment.
Raw material described in the present invention all can commercially availablely obtain, as strongly basic anion exchange resin can use strength triumphant resin in Shanghai to sell the D201 of company limited's production, the products such as 201*7.The product that N-hydroxyethyl perfluorinated octyl sulfuryl amine can adopt Sichuan Hua Gao Chemical Co., Ltd. to produce.The product that 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU) can adopt the biochemical (Shanghai) Co., Ltd. of gill to produce.
Compared with prior art, the present invention has following beneficial effect:
1, good catalyst activity, when preparing solid composite catalyst, N-hydroxyethyl perfluorinated octyl sulfuryl amine, 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), disodium ethylene diamine tetraacetate (EDTA) is as alkaline enhanced aid, can be adsorbed on resin surface, the comprehensive alkalescence of composite catalyst is strengthened, and catalyst activity is better, yield is more than 92%, and selectivity is more than 97%;
2, product is easily separated, the present invention uses solid composite catalyst catalysis tetrafluoroethylene and trifluoroethanol to carry out etherification reaction and obtains 1,1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether product, adopts conventional filter operation just can effective Separation and Recovery solid composite catalyst, enormously simplify product purifying technique;
3, environmental protection, the composite catalyst of recovery can recycle, and effectively decreases the discharge of waste residue, and the present invention not with an organic solvent, to avoid in prior art volatile organic solvent to the pollution of environment.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, but these embodiments are only for explaining the present invention, instead of for limiting the scope of the invention.
Raw material in embodiment all can commercially availablely obtain, and wherein part material is described as follows:
Strongly basic anion exchange resin adopts strength triumphant resin in Shanghai to sell the D201 strongly basic anion exchange resin of company limited's production.
The product that N-hydroxyethyl perfluorinated octyl sulfuryl amine adopts Sichuan Hua Gao Chemical Co., Ltd. to produce.
The product that 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU) adopts the biochemical (Shanghai) Co., Ltd. of gill to produce.
Embodiment 1
A kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
Step 1: add D201 strongly basic anion exchange resin 100Kg in 500L reactor, 300Kg water, the N-hydroxyethyl perfluorinated octyl sulfuryl amine of 0.3Kg, 1, the 8-diazabicyclo (5 of 10Kg, 4,0) 11 carbon-7-alkene (DBU), the disodium ethylene diamine tetraacetate (EDTA) of 0.2Kg, in 60 DEG C of stirring reaction 15h, obtained composite catalyst, for subsequent use.
Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 70Kg is obtained, close charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 60 DEG C, metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 400Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing, rectifying, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selectivity are in table 1.
Embodiment 2
A kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
Step 1: add D201 strongly basic anion exchange resin 100Kg in 500L reactor, the N-hydroxyethyl perfluorinated octyl sulfuryl amine of 200Kg water, 0.1Kg, 1 of 5Kg, 8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), the disodium ethylene diamine tetraacetate (EDTA) of 0.05Kg, in 40 DEG C of stirring reaction 20h, obtained composite catalyst, for subsequent use.
Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 30Kg is obtained, close charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 40 DEG C, metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 300Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing, rectifying, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selectivity are in table 1.
Embodiment 3
A kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
Step 1: add D201 strongly basic anion exchange resin 100Kg in 500L reactor respectively, 400Kg water, the N-hydroxyethyl perfluorinated octyl sulfuryl amine of 0.5Kg, 1, the 8-diazabicyclo (5 of 20Kg, 4,0) 11 carbon-7-alkene (DBU), the disodium ethylene diamine tetraacetate (EDTA) of 0.5Kg, in 80 DEG C of stirring reaction 10h, obtained composite catalyst, for subsequent use.
Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 100Kg is obtained, close charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 80 DEG C, metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 500Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing, rectifying, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selectivity are in table 1.
Embodiment 4
A kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
Step 1: add D201 strongly basic anion exchange resin 100Kg in 500L reactor, 350Kg water, the N-hydroxyethyl perfluorinated octyl sulfuryl amine of 0.4Kg, 1, the 8-diazabicyclo (5 of 15Kg, 4,0) 11 carbon-7-alkene (DBU), the disodium ethylene diamine tetraacetate (EDTA) of 0.4Kg, in 50 DEG C of stirring reaction 12h, obtained composite catalyst, for subsequent use.
Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 80Kg is obtained, close charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 50 DEG C, metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 450Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing, rectifying, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selectivity are in table 1.
Embodiment 5
A kind of preparation method of 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, comprises the following steps:
Step 1: add D201 strongly basic anion exchange resin 100Kg in 500L reactor, 250Kg water, the N-hydroxyethyl perfluorinated octyl sulfuryl amine of 0.2Kg, 1, the 8-diazabicyclo (5 of 7.5Kg, 4,0) 11 carbon-7-alkene (DBU), the disodium ethylene diamine tetraacetate (EDTA) of 0.1Kg, in 70 DEG C of stirring reaction 17h, obtained composite catalyst, for subsequent use.
Step 2: disposablely in 1000L stainless steel autoclave add 100Kg trifluoroethanol, the composite catalyst that the above-mentioned steps (1) of 50Kg is obtained, close charging opening, with the air in nitrogen replacement still, then pass into tetrafluoroethylene monomer, heat up and start reaction, temperature of reaction controls at 70 DEG C, metering passes into the tetrafluoroethylene of reactor, when terminating reaction after the tetrafluoroethylene monomer passing into 350Kg, filtered and recycled composite catalyst, filtrate obtains 1 through washing, rectifying, 1,2,2 ,-four fluoro ethyls-2,2,2-trifluoroethyl ether.Yield and selectivity are in table 1.
Comparative example 1
Step 1 does not add N-hydroxyethyl perfluorinated octyl sulfuryl amine, the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selectivity are in table 1.
Comparative example 2
Step 1 does not add 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU), the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selectivity are in table 1.
Comparative example 3
The potassium hydroxide adding 15% of trifluoroethanol quality in step 2 replaces composite catalyst, the other the same as in Example 1.Obtain 1,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ether products, yield and selectivity are in table 1.
Table 1: the yield of embodiment 1 ~ 3 and comparative example 1 ~ 3 and selectivity
| Embodiment | Yield % | Selectivity .% |
| 1 | 95 | 99 |
| 2 | 93 | 97 |
| 3 | 92 | 98 |
| 4 | 92 | 97 |
| 5 | 97 | 99 |
| Comparative example 1 | 86 | 95 |
| Comparative example 2 | 89 | 92 |
| Comparative example 3 | 81 | 87 |
Claims (3)
1. one kind 1,2,2, the preparation method of-four fluoro ethyl-2,2,2-trifluoroethyl ethers, is characterized in that comprising the following steps:
A () by weight, by strongly basic anion exchange resin 100 parts, 200 ~ 400 parts, water, N-hydroxyethyl perfluorinated octyl sulfuryl amine 0.1 ~ 0.5 part, 1,8-diazabicyclo (5,4,0) 11 5 ~ 20 parts, carbon-7-alkene, disodium ethylene diamine tetraacetate 0.05 ~ 0.5 part, at 40 DEG C ~ 80 DEG C reaction 10 ~ 20h, obtained composite catalyst, for subsequent use;
B () by weight, 100 parts of trifluoroethanols, composite catalyst that 30 ~ 100 parts of steps (1) are obtained are added reactor, then passes into tetrafluoroethylene monomer and react at 40 ~ 80 DEG C, after passing into 300 ~ 500 parts of tetrafluoroethylene monomers, terminate reaction, filtered and recycled composite catalyst, filtrate obtains 1,1,2 through washing to refine, 2,-four fluoro ethyl-2,2,2-trifluoroethyl ethers.
2. the preparation method of according to claim 11,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, it is characterized in that the described temperature of reaction of step (a) is 50 DEG C ~ 70 DEG C, the reaction times is 12 ~ 18h.
3. the preparation method of according to claim 11,1,2,2 ,-four fluoro ethyl-2,2,2-trifluoroethyl ethers, is characterized in that the described temperature of reaction of step (b) is 50 DEG C ~ 70 DEG C.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1550481A (en) * | 2003-05-20 | 2004-12-01 | 大金工业株式会社 | Method for preparing fluoether compound |
| CN1651378A (en) * | 2004-12-27 | 2005-08-10 | 大连振邦氟涂料股份有限公司 | New hydrofluoro ether and its preparation method |
| CN103611570A (en) * | 2013-12-10 | 2014-03-05 | 王金明 | Preparation method of resin catalyst for synthesis of difluoromethyl ether |
| CN103772156A (en) * | 2014-01-06 | 2014-05-07 | 巨化集团技术中心 | Method of continuous catalytic synthesis of 1-alkoxyl-1,1,2,2-tetrafluoroethane in fixed bed |
| CN103980097A (en) * | 2014-05-21 | 2014-08-13 | 芜湖职业技术学院 | Method for synthesizing phenols by etherifying |
| CN104045524A (en) * | 2014-07-10 | 2014-09-17 | 山东中氟化工科技有限公司 | Clean production method for hydrofluoroester |
| CN104971774A (en) * | 2015-07-08 | 2015-10-14 | 王金明 | Preparation method for hydrofluoroether and catalyst thereof |
-
2015
- 2015-07-30 CN CN201510458942.9A patent/CN105061162A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1550481A (en) * | 2003-05-20 | 2004-12-01 | 大金工业株式会社 | Method for preparing fluoether compound |
| CN1651378A (en) * | 2004-12-27 | 2005-08-10 | 大连振邦氟涂料股份有限公司 | New hydrofluoro ether and its preparation method |
| CN103611570A (en) * | 2013-12-10 | 2014-03-05 | 王金明 | Preparation method of resin catalyst for synthesis of difluoromethyl ether |
| CN103772156A (en) * | 2014-01-06 | 2014-05-07 | 巨化集团技术中心 | Method of continuous catalytic synthesis of 1-alkoxyl-1,1,2,2-tetrafluoroethane in fixed bed |
| CN103980097A (en) * | 2014-05-21 | 2014-08-13 | 芜湖职业技术学院 | Method for synthesizing phenols by etherifying |
| CN104045524A (en) * | 2014-07-10 | 2014-09-17 | 山东中氟化工科技有限公司 | Clean production method for hydrofluoroester |
| CN104971774A (en) * | 2015-07-08 | 2015-10-14 | 王金明 | Preparation method for hydrofluoroether and catalyst thereof |
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