CN114656338A - Synthesis method of perfluoro-n-propyl vinyl ether - Google Patents
Synthesis method of perfluoro-n-propyl vinyl ether Download PDFInfo
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- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- RDUGZRZKLLEFFJ-UHFFFAOYSA-N 1-(1,2-dichloro-1,2,2-trifluoroethoxy)-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(Cl)C(F)(F)Cl RDUGZRZKLLEFFJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 11
- LMFJKKGDLAICPF-UHFFFAOYSA-N phenanthrene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC3=CC=CC=C3C2=C1 LMFJKKGDLAICPF-UHFFFAOYSA-N 0.000 claims abstract description 11
- UPVJEODAZWTJKZ-UPHRSURJSA-N (z)-1,2-dichloro-1,2-difluoroethene Chemical group F\C(Cl)=C(/F)Cl UPVJEODAZWTJKZ-UPHRSURJSA-N 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000010189 synthetic method Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- APRDMRHFBGQNEE-UHFFFAOYSA-N FC(C(OC1(C=CC=CC1)F)(F)F)(C(F)(F)F)F Chemical compound FC(C(OC1(C=CC=CC1)F)(F)F)(C(F)(F)F)F APRDMRHFBGQNEE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000382 dechlorinating effect Effects 0.000 claims abstract description 3
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- UMKWCCVQQCRXTM-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropyl hypofluorite Chemical compound FOC(F)(F)C(F)(F)C(F)(F)F UMKWCCVQQCRXTM-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 description 8
- 238000006114 decarboxylation reaction Methods 0.000 description 5
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- -1 salt compound Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYAUGTZMGLUNPS-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)F OYAUGTZMGLUNPS-UHFFFAOYSA-N 0.000 description 1
- DNRSJONRJLBESY-UHFFFAOYSA-N 1,2-dichloro-1,1,2-trifluoroethane Chemical group F[C](Cl)C(F)(F)Cl DNRSJONRJLBESY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C71/00—Esters of oxyacids of halogens
Abstract
The invention provides a synthetic method of perfluoro-n-propyl vinyl ether, which comprises the following steps: (1) reacting pentafluoropropionyl fluoride with fluorine gas under the action of a catalyst to obtain 1-fluorophenoxy heptafluoropropane; (2) 1-oxyfluor heptafluoropropane reacts with 1, 2-difluoro-1, 2-dichloroethylene to obtain 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether; (3) dechlorinating 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether in organic solvent under the action of reducing agent and initiator to obtain perfluoro-n-propyl vinyl ether. The method has the advantages of simple and stable process, less by-products, environmental friendliness, suitability for industrial large-scale production and good economic benefit.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthetic method of perfluoro-n-propyl vinyl ether.
Background
Perfluoro-n-propyl vinyl ether is a comonomer containing fluorine vinyl ether and can participate in polymerization as a copolymerization or modification monomer to change certain properties of the fluoropolymer, such as: low temperature resistance, solvent resistance, toughness, tearing resistance, bonding property with a base material and the like, does not change the original corrosion resistance and aging resistance of the polymer, and has wide application.
At present, the synthesis method of perfluoro-n-propyl vinyl ether mainly comprises the following steps: direct pyrolysis, catalytic pyrolysis, fluorine-containing block method, reduction method, and the like. Wherein, the direct pyrolysis method has simple operation and high yield, is suitable for industrialized production and is a common method for preparation. The direct pyrolysis method generally uses hexafluoropropylene oxide as a raw material, and carries out self-polymerization to generate an acyl fluoride intermediate, and the structure of the vinyl ether is obtained through hydrolysis and salt formation of a metal salt compound, thermal cracking and decarboxylation and the metal fluoride (for example, the method disclosed in Chinese patent ZL 200910229204.1). Wherein, the decarboxylation is a key step of the whole process. Although there are many reports on the decarboxylation method of fluorinated vinyl ether at present, the used catalyst has many disadvantages, for example, the above-mentioned chinese patent ZL200910229204.1 uses silver fluoride catalyst in the decarboxylation process, which is corrosive and toxic, and is not good for safe production; and as the organic amine catalyst is used in Chinese patent ZL200710160650.2 of Zhonghao Chen photochemical research institute, the organic amine catalyst cannot be recycled, and the organic amine catalyst has great influence on the environment. Moreover, the raw material hexafluoropropylene oxide used is expensive, which results in higher production cost.
Therefore, the method for further exploring and researching the synthetic method of the perfluoro-n-propyl vinyl ether, which has the advantages of simple and stable process, less by-products and environmental friendliness, has important significance.
Disclosure of Invention
In order to solve the problems, the invention provides a novel synthesis method of perfluoro-n-propyl vinyl ether, which is different from the existing synthesis method. There is no step of forming a salt by hydrolysis of a metal salt compound, no step of thermal decarboxylation and metal fluoride, and no use of a methylsiloxane-series catalyst or an organic amine catalyst.
The invention provides a synthetic method of perfluoro-n-propyl vinyl ether, which comprises the following steps:
(1) reacting pentafluoropropionyl fluoride with fluorine gas under the action of a catalyst to obtain 1-fluorophenoxy heptafluoropropane;
(2) reacting 1-fluoroxyheptafluoropropane with 1, 2-difluoro-1, 2-dichloroethylene to obtain 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether;
(3) dechlorinating 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether in an organic solvent under the action of a reducing agent and an initiator to obtain perfluoro-n-propyl vinyl ether;
the reaction formula is as follows:
CF3 CF2COF+F2——→CF3 CF2 CF2OF
CF3 CF2 CF2OF+CFCl＝CFCl——→CF3 CF2 CF2OCFClCF2Cl
CF3 CF2 CF2OCFClCF2Cl+Zn——→CF3 CF2 CF2OCF＝CF2+ZnCl2。
further, the catalyst of step (1) is an alkali metal fluoride;
and/or the reducing agent in the step (3) is zinc, the initiator is zinc chloride, and the organic solvent is one or more of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and poly (perfluoroisopropyl ether) oil.
Further, the catalyst in the step (1) is one or more of NaF, KF, NaF, CsF and LiF;
and/or, the organic solvent in the step (3) is dimethylformamide.
Further, in the reaction in the step (1), fluorine gas diluted by pentafluoropropionyl fluoride and nitrogen gas is introduced into the reactor A added with the catalyst for reaction; the rate ratio of fluorine gas diluted by pentafluoropropionyl fluoride and nitrogen gas introduced into the reactor is 200 (10-500); the fluorine gas diluted with nitrogen gas has a fluorine gas content of 40% to 99%, preferably 40% to 85%.
Further, the reaction conditions in step (1) are as follows: the temperature is 60-450 ℃, and the pressure is 0-0.1 MPa; preferably, the reaction temperature is 100-400 ℃.
Further, the reaction in the step (2) is to introduce 1-fluoroxyheptafluoropropane into a reactor B added with 1, 2-difluoro-1, 2-dichloroethylene at a rate of 10-500L/h for reaction, wherein the 1, 2-difluoro-1, 2-dichloroethylene accounts for 30-80% of the volume of the reactor B.
Further, the reaction conditions in step (2) are as follows: the temperature is-30 ℃ to-0 ℃, and the reaction is 0-0.12 MPa; preferably: the temperature is-25 to-10 ℃, and the reaction is 0 to 0.1 MPa.
Further, the molar ratio of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether, the reducing agent and the organic solvent in the step (3) is 1 (3-4) to (8-10), and the using amount of the initiator is 3-7% of the mass of the reducing agent; preferably, the molar ratio of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether to the reducing agent to the organic solvent is 1:3:8, and the amount of the initiator is 5% of the mass of the reducing agent.
Further, the reaction in the step (3) is that the organic solvent, the reducing agent and the initiator are added into a reactor C, and then the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether is continuously added into the reactor C;
the organic solvent accounts for 30-70% of the volume of the reactor C, and the adding rate of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether is as follows: 300-600 g of 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether is added into every 5L of organic solvent every hour.
Further, the reaction conditions in step (3) are as follows: the temperature is 40-100 ℃, the pressure is 0.05-0.1 MPa, and preferably, the reaction conditions further comprise stirring at a speed of 80-300 r/min.
The invention has the beneficial effects that: (1) the synthetic method has simple process, few byproducts and environmental protection; (2) the method is suitable for large-scale production, can stably prepare the perfluoro-n-propyl vinyl ether with high purity, and has good industrial prospect; (3) the raw material pentafluoropropionyl fluoride for synthesizing the fluorine-n-propyl vinyl ether has wide sources, can be derived from byproducts or wastes in the production process of other chemical products (such as waste gas in the process of synthesizing the perfluoropolyether acid), realizes waste utilization, and has good economic benefit.
The inert gas refers to a gas simple substance corresponding to all group 0 elements on the periodic table of elements.
It will be apparent that various other modifications, substitutions and alterations can be made in the present invention without departing from the basic technical concept of the invention as described above, according to the common technical knowledge and common practice in the field.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a process flow of the present invention.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
Example 1 Synthesis of perfluoro-n-propyl vinyl Ether according to the invention
(1) Adding catalyst NaF into the reactor, and then electrolyzing the fluorine gas (F)2) After diluting to 40% (v/v) with nitrogen, the reaction mixture was introduced into a reactor A at a flow rate of 500L/h, and pentafluoropropionyl fluoride (CF) was added3CF2COF) is introduced into a reactor A at a rate of 200L/h, the reaction temperature is controlled to be 100-400 ℃, and the reaction pressure is controlled to be 0-0.1 MPa.
(2) The reacted gas enters a reactor B at the flow rate of about 500L/h to perform addition reaction with 1, 2-difluoro-1, 2-dichloroethylene (CFCl) to prepare an intermediate product 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropaneEther (CF)3CF2CF2OCFClCF2Cl); the volume of the 1, 2-difluoro-1, 2-dichloroethylene accounts for 30 to 80 percent of that of the reactor B. The reaction temperature is controlled to be-25 ℃ to-10 ℃, and the reaction pressure is controlled to be 0-0.1 MPa.
(3) Intermediate CF3CF2CF2OCFClCF2And (3) performing dechlorination reaction by using Cl: the dechlorination kettle used in the dechlorination reaction is a GSH type magnetic stirring reaction kettle which is provided with a reflux device, and the rotating speed of the stirrer in the reaction is 300 r/min.
1) Adding an organic solvent dimethylformamide with the volume of 50% of that of the dechlorination reaction kettle, then adding zinc powder and zinc chloride with the weight of 5% of that of the zinc powder, and heating to 70 ℃.
2) Adding CF into the reaction kettle3CF2CF2OCFClCF2Cl, and reacting at 70 ℃ under 0.05-0.1 MPa; wherein CF3CF2CF2OCFClCF2The mol ratio of Cl, zinc powder and organic solvent is 1:3: 8; according to the volume of the organic solvent of 5L, CF3CF2CF2OCFClCF2Cl was added at a rate of 400 g/h.
And (3) passing a gas-phase product obtained in the dechlorination reaction kettle through a reflux condenser, collecting the gas-phase product in a perfluoro-n-propyl vinyl ether crude monomer collecting bottle, and placing the collecting bottle in a-45 ℃ cold trap. The purity of the obtained crude monomer is more than or equal to 90 percent, and the yield reaches more than 70 percent.
The perfluoro-n-propyl vinyl ether crude monomer is purified by a rectifying tower to obtain perfluoro-n-propyl vinyl ether with the concentration of more than or equal to 99.95 percent, and the operating pressure of the rectifying tower is controlled below 0.1 MPa.
Example 2 Synthesis of perfluoro-n-propyl vinyl Ether according to the invention
The catalyst of step (1) was replaced with KF, and the remaining steps were the same as in example 1. The purity of the prepared crude monomer is more than or equal to 90 percent, and the yield can reach more than 70 percent. The perfluoro-n-propyl vinyl ether crude monomer is purified by a rectifying tower to obtain perfluoro-n-propyl vinyl ether with the concentration of more than or equal to 99.95 percent, and the operating pressure of the rectifying tower is controlled below 0.1 MPa.
Example 3 Synthesis of perfluoro-n-propyl vinyl Ether according to the invention
The catalyst in the step (1) was replaced with CsF, and the fluorine gas concentration was 85% (v/v) after diluting the fluorine gas with nitrogen gas, and the rest of the steps were the same as in example 1. The purity of the prepared crude monomer is more than or equal to 90 percent, and the yield can reach more than 70 percent. The perfluoro-n-propyl vinyl ether crude monomer is purified by a rectifying tower to obtain perfluoro-n-propyl vinyl ether with the concentration of more than or equal to 99.95 percent, and the operating pressure of the rectifying tower is controlled below 0.1 MPa.
In conclusion, the invention provides a brand new synthesis method of perfluoro-n-propyl vinyl ether, which takes pentafluoropropionyl fluoride with wide sources as raw materials, prepares the perfluoro-n-propyl vinyl ether with high purity through a simple, stable and environment-friendly reaction process, is suitable for industrial large-scale production, and has good economic benefit.
Claims (10)
1. A synthetic method of perfluoro-n-propyl vinyl ether is characterized by comprising the following steps:
(1) reacting pentafluoropropionyl fluoride with fluorine gas under the action of a catalyst to obtain 1-fluorophenoxy heptafluoropropane;
(2) 1-oxyfluor heptafluoropropane reacts with 1, 2-difluoro-1, 2-dichloroethylene to obtain 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether;
(3) dechlorinating 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether in an organic solvent under the action of a reducing agent and an initiator to obtain perfluoro-n-propyl vinyl ether;
the reaction formula is as follows:
CF3CF2COF+F2——→CF3CF2CF2OF
CF3CF2CF2OF+CFCl＝CFCl——→CF3CF2CF2OCFClCF2Cl
CF3CF2CF2OCFClCF2Cl+Zn——→CF3CF2CF2OCF＝CF2+ZnCl2。
2. the method of synthesis of claim 1, wherein the catalyst of step (1) is an alkali metal fluoride;
and/or the reducing agent in the step (3) is zinc, the initiator is zinc chloride, and the organic solvent is one or more of dimethyl sulfoxide, dimethylformamide, dimethylacetamide and poly-perfluoroisopropyl ether oil.
3. The method of claim 2, wherein the catalyst of step (1) is one or more of NaF, KF, NaF, CsF, LiF;
and/or, the organic solvent in the step (3) is dimethylformamide.
4. The synthesis method according to claim 1, wherein the reaction in step (1) is that pentafluoropropionyl fluoride and fluorine gas diluted with nitrogen gas are introduced into a reactor A to which a catalyst is added; the rate ratio of fluorine gas diluted by pentafluoropropionyl fluoride and nitrogen gas introduced into the reactor is 200 (10-500); the fluorine gas diluted with nitrogen gas has a fluorine gas content of 40% to 99%, preferably 40% to 85%.
5. The synthesis process according to claim 1 or 4, characterized in that the reaction conditions of step (1) are: the temperature is 60-450 ℃, and the pressure is 0-0.1 MPa; preferably, the reaction temperature is 100-400 ℃.
6. The synthetic method of claim 1, wherein the reaction in step (2) is performed by introducing 1-fluoroxyheptafluoropropane into a reactor B into which 1, 2-difluoro-1, 2-dichloroethylene is added at a rate of 10 to 500L/h, and the 1, 2-difluoro-1, 2-dichloroethylene accounts for 30 to 80 percent of the volume of the reactor B.
7. The synthesis method according to claim 1 or 6, wherein the reaction conditions in step (2) are as follows: the temperature is-30 ℃ to-0 ℃, and the reaction is 0-0.12 MPa; preferably: the temperature is-25 to-10 ℃, and the reaction is 0 to 0.1 MPa.
8. The synthesis method of claim 1, wherein the molar ratio of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether, the reducing agent and the organic solvent in the step (3) is 1 (3-4) to (8-10), and the amount of the initiator is 3-7% of the mass of the reducing agent; preferably, the molar ratio of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether to the reducing agent to the organic solvent is 1:3:8, and the amount of the initiator is 5% of the mass of the reducing agent.
9. The method of claim 8, wherein the reaction of step (3) is carried out by adding the organic solvent, the reducing agent and the initiator into the reactor C, and then continuously adding 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether into the reactor C;
the organic solvent accounts for 30-70% of the volume of the reactor C, and the adding rate of the 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether is as follows: 300-600 g of 1, 2-dichloro-1, 2, 2-trifluoroethyl heptafluoropropyl ether is added into every 5L of organic solvent every hour.
10. The synthesis process according to any one of claims 1, 8 and 9, wherein the reaction conditions in step (3) are as follows: the temperature is 40-100 ℃, the pressure is 0.05-0.1 MPa, and preferably, the reaction conditions further comprise stirring at a speed of 80-300 r/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115246766A (en) * | 2022-08-29 | 2022-10-28 | 四川弘氟新材料有限公司 | Method for treating fluorinated tail gas in perfluoropolyether synthesis process |
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| CN107286060A (en) * | 2017-06-22 | 2017-10-24 | 山东华夏神舟新材料有限公司 | End group is the preparation method of the perfluoroalkyl vinyl ether of sulfonyl fluoride group |
| CN107298647A (en) * | 2017-06-22 | 2017-10-27 | 山东华夏神舟新材料有限公司 | End group is the preparation method of the straight chain perfluoroalkyl vinyl ether of sulfonyl fluoride group |
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| CN85101757A (en) * | 1984-10-16 | 1987-01-31 | 大金工业株式会社 | The method for preparing fluor containing polyethers |
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| CN107298647A (en) * | 2017-06-22 | 2017-10-27 | 山东华夏神舟新材料有限公司 | End group is the preparation method of the straight chain perfluoroalkyl vinyl ether of sulfonyl fluoride group |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115246766A (en) * | 2022-08-29 | 2022-10-28 | 四川弘氟新材料有限公司 | Method for treating fluorinated tail gas in perfluoropolyether synthesis process |
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Correction item: Applicant Correct: SICHUAN DAOHONG NEW MATERIALS Co.,Ltd. False: Sichuan Daohong New Material Co.,Ltd. Number: 25-02 Page: The title page Volume: 38 Correction item: Applicant Correct: SICHUAN DAOHONG NEW MATERIALS Co.,Ltd. False: Sichuan Daohong New Material Co.,Ltd. Number: 25-02 Volume: 38 |