CN112079758B - Preparation method of perfluoroalkyl acyl peroxide - Google Patents
Preparation method of perfluoroalkyl acyl peroxide Download PDFInfo
- Publication number
- CN112079758B CN112079758B CN202010875267.0A CN202010875267A CN112079758B CN 112079758 B CN112079758 B CN 112079758B CN 202010875267 A CN202010875267 A CN 202010875267A CN 112079758 B CN112079758 B CN 112079758B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- ionic liquid
- temperature
- fluoride
- peroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a preparation method of perfluoroalkyl acyl peroxide, which comprises the following steps: adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0-15 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0-15 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide. The invention uses perfluoro or polyfluoro solvent to replace the ozone-consuming substance CFC113, avoids the adverse effect existing in the application of CFC113, is more superior in the aspects of safety and environmental protection, and uses the titanium-silicon molecular sieve ionic liquid composite catalyst, so that the product yield is higher; the perfluoroalkyl acyl peroxide obtained by the invention is used as an initiator to prepare TFE/HFP polymer, has better thermal stability and mechanical and physical properties, has high production capacity of the copolymer in unit reactor volume, can be used for processing cable insulation, films, pipes, fibers, plates, powder spraying and the like, and can be used in the fields of electronics, chemical engineering, aviation, radio, medicine and the like.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a preparation method of perfluoroalkyl acyl peroxide.
Background
The polymer chains formed when commonly used inorganic peroxides such as Ammonium Persulfate (APS), potassium persulfate (KPS) are used as initiators in fluoropolymer synthesis are unstable, causing problems of decomposition during material processing and aggregation to generate bubbles. The terminal fluorine-containing organic peroxide can be used in the synthesis of a fluoropolymer and the above-mentioned problems cannot be avoided.
U.S. Pat. No. 3,3528954, published 1970, 09, 15, discloses a low temperature initiator bis-perfluoropropionyl peroxide (3P) with a polymerization temperature of 60 deg.C, an initiator solvent of CFC113(1, 1, 2-trifluorotrichloroethane) and a solution concentration of 0.0025 g/mL. U.S. Pat. No. 3,217,510, published 1972, 06,20, discloses initiators which are bis- (1, 2, 4-trichlorotrifluorohexanoyl) peroxide (dissolved in CFC 113), with a solution concentration of 0.82g/mL and a polymerization temperature of 25 ℃. The initiator of Chinese patent CN1483747 published as 24.03.2004 is perfluorinated cyclohexyl acyl peroxide, the reaction temperature is 20-50 ℃, the initiator solvent is CFC113, and the solution concentration is 12%. U.S. Pat. No. 5,342,342, 1993, No. 01/26 discloses the use of 1, 1, 2, 2-tetrafluorocyclohexane as an initiator solvent at a solution concentration of 0.05M and a polymerization temperature of 33-35 ℃.
Russian patent RU2195465, published 12, 2002 and 27, discloses the preparation of copolymers of Tetrafluoroethylene (TFE) and perfluoropropyl vinyl ether (PFPVE) in which the initiator solvents are perfluoromethylcyclohexane, 1-hydro-4-chloro-octafluorobutane and perfluoropropyl vinyl ether, and the content of perfluorodiacyl peroxide in the selected solvent is 5-10% by weight, wherein the perfluorodiacyl peroxide is perfluorodicyclohexyl fluoride peroxide. The preparation process of the initiator comprises the following steps: a stirring device and a reagent meter are arranged in a glass container cooled by saline water. The initiator is obtained by the interaction of a mixture of perfluorocyclohexyl formyl fluoride, 32 wt% of aqueous hydrogen peroxide solution and 17 wt% of aqueous sodium hydroxide solution in an organic solvent perfluoromethylcyclohexane (Freon 350) at the temperature of between 10 ℃ below zero and 15 ℃ below zero. At the end of the reaction, the organic layer was separated from the aqueous layer and washed with cooling water. The obtained perfluorodicyclohexyl acyl peroxide dissolved in Freon 350 was analyzed by an iodine amount.
CFC113 is used in the above invention and the prior art preparation method, and the substance is an ozone-consuming substance, which has serious potential safety hazard to the environment.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing perfluoroalkyl acyl peroxide.
The invention previously filed by the applicant, CN101786977A, discloses a preparation method of perfluoroalkyl acyl peroxide, which is further improved on the basis of the patent and uses a titanium silicalite ionic liquid composite catalyst to replace inorganic base.
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 27.5-35% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0-15 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0-15 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
Fluorine-containing acid halide compound (R) f COX, wherein R f Is perfluoroalkyl, X is chlorine or fluorine) with sodium hydroxide (NaOH), hydrogen peroxide (H) 2 O 2 ) The reaction can generate perfluoroalkyl acyl peroxide ((R) f CO 2 ) 2 ) For example, at-8 to-5 ℃ C, CFC113 (CF) 2 ClCFCl 2 ) As solvent, perfluoroacyl halide (chlorine or fluorine), NaOH and H 2 O 2 In a molar ratio of 2: 1, the reaction equation is as follows:
furthermore, the titanium silicalite molecular sieve ionic liquid composite catalyst uses a titanium silicalite molecular sieve modified by vinyl trimethoxy silane as a raw material;
further, the preparation method of the vinyltrimethoxysilane modified titanium silicalite molecular sieve comprises the following steps:
according to the mass parts, 40-80 parts of titanium silicalite molecular sieve, 1-6 parts of vinyl trimethoxy silane and 1200 parts of water are stirred and reacted for 3-8 hours at the temperature of 70-90 ℃ to obtain the vinyl trimethoxy silane modified titanium silicalite molecular sieve.
The titanium silicalite molecular sieve has a large number of hydroxyl groups on the surface, and the structural formula of the titanium silicalite molecular sieve grafted by vinyl siloxane is shown as follows:
further, the titanium silicalite molecular sieve ionic liquid composite catalyst combines 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt ionic liquid with a titanium silicalite molecular sieve grafted by vinyl siloxane through hydrosilylation reaction.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
according to the mass parts, under the nitrogen atmosphere, 30-40 parts of tetramethyldisilazane, 3-6 parts of 15% -20% isopropanol solution of chloroplatinic acid, 0.02-0.5 part of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 1000-2000 parts of isopropanol are added into a reaction kettle, uniformly stirred and mixed, then the 280 parts of vinylsiloxane grafted titanium-silicon molecular sieve of 120-plus type is added into the reaction kettle under stirring, stirred at 60-70 ℃ for 10-20h, then the temperature is controlled at 110-plus type and the isopropanol is evaporated at 120 ℃, the obtained solid is treated in an oven at 100-plus type and 150 ℃ for 1-3h, and the titanium-silicon molecular sieve ionic liquid composite catalyst is obtained.
Further, the perfluoro or polyfluoro organic solvent of the present invention is decafluoropentane, pentafluorodichloropropane, hexafluoropropylene dimer, hexafluoropropylene trimer, dichlorooctafluorobutane or perfluorotributylamine.
Furthermore, the mass ratio of the perfluoroalkyl acyl fluoride to the titanium silicalite molecular sieve ionic liquid composite catalyst is 1: 0.05-0.1.
Furthermore, the molar ratio of the perfluoroalkyl acyl fluoride to the hydrogen peroxide is 2.00: 1.35-1.37, and under the condition, the obtained perfluoroalkyl acyl peroxide has higher reaction yield.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-5 to-10 ℃.
Furthermore, the reaction temperature is-5 to-10 ℃ in the process of adding the perfluoroalkyl acyl fluoride into the system.
Further, the perfluoroalkyl acyl fluoride of the present invention may be perfluorocyclohexyl acyl fluoride, perfluoro-2-methyl-3-oxahexanoyl fluoride or perfluoro-2.5-dimethyl-3.6-dioxanonanoyl fluoride.
The polymerization was carried out by the process described in CN 1483747. Copolymerizing the mixture of TFE and HFP in monomer medium HFP or in a fluorine-containing atmosphere ozone-safe solvent at 25-50 deg.C under 1.1-1.5 MPa with a perfluorinated initiator group as initiator, the preliminary and additional mixtures are used during the polymerization, the unreacted monomers are subsequently removed and the copolymer powder obtained is heated to remove residual initiator, after the copolymerization process is finished, the reactant is cooled to the pressure of 0.3-1.0 MPa, and then the reactant is pressed or transferred to a closed space with the pressure of 0.05-0.1 MPa lower than that of the reaction area, then separating and removing unreacted monomers and solvents of post-treatment equipment under the stirring condition through a temperature programming process, firstly heating to 50-60 ℃, then, the separation is carried out at 120-200 ℃, and then the obtained copolymer powder is heated for 3-4 hours at 120-200 ℃. The unreacted monomer and the solvent are separated at a pressure of 0.2 to 0.3MPa when the temperature is raised to 50 to 60 ℃ and at a pressure of 0.09 to 0.11MPa when the temperature is raised to 120-200 ℃ and the monomer is periodically discharged when the pressure is higher than 0.1 to 0.12 MPa. The copolymer powder is heated at 120 to 180 ℃ and preferably under a residual pressure of 20 to 40mm Hg. A pre-mixture is used in the copolymerization of TFE and HFP, wherein the pre-mixture contains 80-86% of HFP and 14-20% mol of TFE, and the supplemented mixture contains 12-15% of HFP and 85-88% of TFE. The solvent used for the polymerization is preferably perfluorocyclobutane, which is an atmospheric ozone-safe solvent. The molecular weight regulator used for the copolymerization is, for example, methanol. The polymerization rate is 54 g/Lh-74 g/Lh.
Compared with the prior art, the invention has the beneficial effects that: the invention uses perfluoro or polyfluoro solvent to replace the ozone-depleting substance CFC113, avoids the adverse effect of the application of the CFC113 and has better safety and environmental protection. The invention uses a mesoporous magnetic titanium silicalite molecular sieve ionic liquid composite catalyst to carry out catalytic reaction, can effectively improve the yield of the product, and the catalyst can be recovered, is convenient to separate and is more convenient to use; the TFE/HFP polymers prepared using the perfluoroalkyl acyl peroxides obtained in the present invention as initiator can be made into products such as films and tubes, which are substantially free of gels and which ensure high quality products (e.g., cable insulation, films and fibers for electrical applications). The process of the present invention allows to obtain TFE and HFP copolymers of wide grades (melt index from 2 to 15g/10min, even up to 30g/10min), better thermal stability, higher mechanical and physical properties index, and higher production capacity of the copolymer per unit reactor volume. The copolymers obtained by the process of the invention can be processed to prepare cable insulations, films, tubes, fibers, plates, powder coatings and the like, and can be used in the fields of electronics, chemical engineering, aviation, radio, medicine and other national economy.
Drawings
FIG. 1 is a Fourier infrared spectrum of a sample of the titanium silicalite ionic liquid composite catalyst prepared in example 2.
At 459cm -1 An absorption peak of a titanium-oxygen bond at 1079/789cm is present in the vicinity -1 An antisymmetric stretching/symmetric stretching absorption peak of a silicon-oxygen bond exists nearby, which indicates that the vinyl siloxane grafted titanium-silicon molecular sieve participates in the reaction; at 2922cm -1 The expansion vibration absorption peak of the hydrocarbon exists nearby and is 683cm -1 An absorption peak of silicon carbon at 942cm is present in the vicinity -1 An absorption peak of silicon nitrogen exists nearby, which indicates that tetramethyldisilazane participates in the reaction; at 1585cm -1 An absorption peak of a carbon-nitrogen single bond in the vicinity of 1256cm -1 An antisymmetric telescopic absorption peak of a carbon-fluorine bond exists nearby, which indicates that the 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
the peroxide content was determined by iodometry. And (3) measuring the surface alkali content of the solid alkali by adopting an adsorption indicator benzoic acid titration method.
Quality control indexes are as follows: the content of the perfluoroalkyl acyl peroxide is 16.0-20.0%, and the content of the perfluoroalkyl acyl fluoride is less than or equal to 0.15%.
Measurement of Perfluoroalkylacyl peroxide content
To a 100 mL conical flask with a stopper was added 10 mL of glacial acetic acid, supplemented with (2. + -. 0.5) g of potassium iodide and 1 mL of the analytical sample was pipetted, left in the dark for 10 minutes and then titrated with 0.1mol/L sodium thiosulfate solution until colorless became an end point.
Result processing
The mass percent of the perfluoroalkanoyl peroxide in the organic layer is calculated according to the following formula:
x = c · V × 0.325 × 100/(ρ · V sample)
In the formula:
c, the concentration of the standard titration solution of sodium thiosulfate is in mol/L;
v is the volume of the sodium thiosulfate standard titration solution used for titration consumption, and the unit is mL;
0.325 — mass of perfluoroalkylacyl peroxide, expressed in grams, in g, equivalent to 1 mL of sodium thiosulfate standard solution [ C (Na2S2O3) =1mol/L ];
sample V-sample volume in mL;
ρ -the density of the sample solution in g/mL.
Measurement of perfluoroalkyl acyl fluoride content
About 50mL of distilled water (water temperature below 5 ℃) was added to a 250mL conical flask with a plug mill, 5.0 mL of the analyte was added rapidly, the flask was placed on a magnetic stirrer and stirred for 5 minutes, 3 to 4 drops of 10g/L phenolphthalein were added, the solution was titrated with 0.1mol/L sodium hydroxide standard titration solution until the occurrence of a slight rose-red color was not changed within one minute to the end point of titration, and the volume of the sodium hydroxide standard titration solution consumed was recorded.
Result processing
The content of perfluoroalkyl acyl fluoride in the sample, expressed as mass percent, is calculated according to the following formula:
x = c · V × 0.164 × 100/(ρ · V sample)
In the formula:
c-concentration of sodium hydroxide standard titration solution in moles per liter (mol/L);
v-volume of standard titration solution of sodium hydroxide consumed for titration in milliliters (mL);
0.164 — mass of perfluoroalkylacyl fluoride, expressed in grams, in grams (g), equivalent to 1 mL of sodium hydroxide standard solution [ c (naoh) =1mol/L ];
ρ -the density of the sample in grams per milliliter (g/mL).
V sample-volume of sample consumed for analysis in milliliters (mL).
Example 1
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding a titanium silicalite molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 27.5% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
The preparation method of the vinyltrimethoxysilane modified titanium silicalite molecular sieve comprises the following steps:
40g of titanium silicalite molecular sieve, 1g of vinyl trimethoxy silane and 1200g of water are stirred and reacted for 3 hours at the temperature of 70 ℃, and the vinyl trimethoxy silane modified titanium silicalite molecular sieve is obtained after the reaction.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
under the nitrogen atmosphere, 30g of tetramethyldisilazane, 3g of isopropanol solution of chloroplatinic acid with the mass percent concentration of 15%, 0.02g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 1000g of isopropanol are added into a reaction kettle, after stirring and mixing uniformly, 120g of vinylsiloxane grafted titanium silicalite molecular sieve is added into the reaction kettle while stirring, the mixture is stirred for 10 hours at the temperature of 60 ℃, then the temperature is controlled to be 110 ℃, the isopropanol is removed by evaporation, and the obtained solid is treated for 1 hour in an oven at the temperature of 100 ℃ to obtain the titanium silicalite molecular sieve ionic liquid composite catalyst.
Further, the perfluoro or polyfluoro organic solvent of the present invention is decafluoropentane.
Further, the mass ratio of the perfluoroalkyl acyl fluoride to the titanium silicalite molecular sieve ionic liquid composite catalyst is 1: 0.05.
Further, the molar ratio of the perfluoroalkyl acyl fluoride and hydrogen peroxide is 2.00: 1.35.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-5 ℃.
Further, the perfluoroalkyl acyl fluoride is added into the system, and the reaction temperature is-5 ℃.
Further, the perfluoroalkyl acyl fluoride of the invention is perfluorocyclohexyl acyl fluoride.
The yield of peroxide product generated in this experimental example was 97.9%.
Example 2
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 31.5% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of-8 ℃; continuously adding perfluoroalkyl acyl fluoride at the temperature of-5 ℃ for reaction; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
The preparation method of the vinyltrimethoxysilane modified titanium silicalite molecular sieve comprises the following steps:
60g of titanium silicalite molecular sieve, 3g of vinyl trimethoxy silane and 1400g of water are stirred and reacted for 7 hours at the temperature of 72 ℃, and the vinyl trimethoxy silane modified titanium silicalite molecular sieve is obtained after the reaction.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
under the nitrogen atmosphere, 35g of tetramethyldisilazane, 4g of an isopropanol solution of chloroplatinic acid with the mass percent concentration of 18%, 0.09g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 1100g of isopropanol are added into a reaction kettle, uniformly stirred and mixed, 170g of vinylsiloxane grafted titanium silicalite molecular sieve is added into the reaction kettle under stirring, stirred for 15 hours at 65 ℃, then the temperature is controlled at 113 ℃ to evaporate and remove the isopropanol, and the obtained solid is treated in an oven at 100 ℃ for 1.2 hours, so that the titanium silicalite molecular sieve ionic liquid composite catalyst is obtained.
Further, the perfluoro or polyfluoro organic solvent of the present invention is pentafluorodichloropropane.
Further, the mass ratio of the perfluoroalkyl acyl fluoride to the titanium silicalite molecular sieve ionic liquid composite catalyst is 1: 0.08.
Further, the molar ratio of the perfluoroalkyl acyl fluoride and hydrogen peroxide is 2.00: 1.36.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-8 ℃.
Further, in the process of adding the perfluoroalkyl acyl fluoride into the system, the reaction temperature is-8 ℃.
Further, the perfluoroalkyl acyl fluoride of the invention is perfluoro-2-methyl-3-oxahexanoyl fluoride.
The yield of peroxide product generated in this experimental example was 98.4%.
Example 3
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 35% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of-15 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of-15 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
The preparation method of the vinyltrimethoxysilane modified titanium silicalite molecular sieve comprises the following steps:
80g of titanium silicalite molecular sieve, 6g of vinyl trimethoxy silane and 1600g of water are stirred and reacted for 8 hours at the temperature of 90 ℃, and the vinyl trimethoxy silane modified titanium silicalite molecular sieve is obtained after the reaction.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
under the nitrogen atmosphere, 40g of tetramethyldisilazane, 6g of isopropanol solution of chloroplatinic acid with the mass percent concentration of 20%, 0.5g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 2000g of isopropanol are added into a reaction kettle, after uniform stirring and mixing, 280g of vinylsiloxane grafted titanium silicalite molecular sieve is added into the reaction kettle under stirring, the mixture is stirred for 20 hours at 70 ℃, then the temperature is controlled to 120 ℃, the isopropanol is removed through evaporation, and the obtained solid is treated for 3 hours in an oven at 150 ℃ to obtain the titanium silicalite ionic liquid composite catalyst.
Further, the perfluoro or polyfluoro organic solvent of the present invention is hexafluoropropylene dimer.
Further, the mass ratio of the perfluoroalkyl acyl fluoride to the titanium silicalite molecular sieve ionic liquid composite catalyst is 1: 0.1.
Further, the molar ratio of the perfluoroalkyl acyl fluoride and hydrogen peroxide is 2.00: 1.37.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-10 ℃.
Further, the perfluoroalkyl acyl fluoride is added into the system, and the reaction temperature is-10 ℃.
Further, the perfluoroalkyl acyl fluoride of the present invention is perfluoro-2, 5-dimethyl-3, 6-dioxanonanoyl fluoride.
The yield of peroxide product generated in this experimental example was 99.1%.
Comparative example 1
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding sodium hydroxide and 27.5 percent hydrogen peroxide solution into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
Further, the perfluoro or polyfluoro organic solvent of the present invention is decafluoropentane.
Further, the mass ratio of the perfluoroalkyl acyl fluoride to the sodium hydroxide is 1: 0.05.
Further, the molar ratio of the perfluoroalkyl acyl fluoride and hydrogen peroxide is 2.00: 1.35.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-5 ℃.
Further, the perfluoroalkyl acyl fluoride is added into the system, and the reaction temperature is-5 ℃.
Further, the perfluoroalkyl acyl fluoride of the invention is perfluorocyclohexyl acyl fluoride.
The yield of peroxide product generated in this experimental example was 68.1%.
Comparative example 2
A preparation method of perfluoroalkyl acyl peroxide mainly adopts the following scheme:
adding a titanium silicalite molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 27.5% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0 ℃; then separating and washing the organic solvent layer to obtain the perfluoroalkyl acyl peroxide.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
under the nitrogen atmosphere, 30g of tetramethyldisilazane, 3g of isopropanol solution of chloroplatinic acid with the mass percent concentration of 15%, 0.02g of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 1000g of isopropanol are added into a reaction kettle, after uniform stirring and mixing, 120g of titanium silicalite molecular sieve is added into the reaction kettle under stirring, the stirring is carried out for 10 hours at 60 ℃, then the temperature is controlled at 110 ℃ to evaporate and remove the isopropanol, and the obtained solid is treated in an oven at 100 ℃ for 1 hour to obtain the titanium silicalite molecular sieve ionic liquid composite catalyst.
Further, the perfluoro or polyfluoro organic solvent of the present invention is decafluoropentane.
Further, the mass ratio of the perfluoroalkyl acyl fluoride to the titanium silicalite molecular sieve ionic liquid composite catalyst is 1: 0.05.
Further, the molar ratio of the perfluoroalkyl acyl fluoride and hydrogen peroxide is 2.00: 1.35.
Further, the reaction temperature of the sodium hydroxide solution and the hydrogen peroxide solution is-5 ℃.
Further, the perfluoroalkyl acyl fluoride is added into the system, and the reaction temperature is-5 ℃.
Further, the perfluoroalkyl acyl fluoride of the invention is perfluorocyclohexyl acyl fluoride.
The yield of peroxide product generated in this experimental example was 84.3%.
Comparative example 3
The preparation method of the vinyltrimethoxysilane modified titanium silicalite molecular sieve comprises the following steps:
40g of titanium silicalite molecular sieve, 1g of vinyl trimethoxy silane and 1200g of water are stirred and reacted for 3 hours at the temperature of 70 ℃, and the vinyl trimethoxy silane modified titanium silicalite molecular sieve is obtained after the reaction.
The preparation method of the titanium silicalite molecular sieve ionic liquid composite catalyst comprises the following steps:
under the atmosphere of nitrogen, adding 30g of tetramethyldisilazane, 3g of isopropanol solution of chloroplatinic acid with the mass percent concentration of 15% and 1000g of isopropanol into a reaction kettle, stirring and mixing uniformly, adding 120g of vinylsiloxane grafted titanium silicalite molecular sieve into the reaction kettle under stirring, stirring for 10 hours at 60 ℃, then controlling the temperature to 110 ℃ and evaporating to remove the isopropanol, and treating the obtained solid in an oven at 100 ℃ for 1 hour to obtain the titanium silicalite ionic liquid composite catalyst.
Otherwise, the same as example 1;
the yield of peroxide product generated in this experiment was 81.1%.
Claims (7)
1. A preparation method of perfluoroacyl peroxide is technically characterized by comprising the following steps: adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 27.5-35% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0-15 ℃; then continuously adding perfluoroalkyl acyl fluoride to react at the temperature of 0-15 ℃; then separating and washing the organic solvent layer to obtain perfluoroalkyl acyl peroxide; or: adding a titanium-silicon molecular sieve ionic liquid composite catalyst and a hydrogen peroxide solution with the mass percent concentration of 27.5-35% into a perfluorinated or polyfluorinated organic solvent, and reacting at the temperature of 0-15 ℃; then continuously adding perfluoro-2-methyl-3-oxahexanoyl fluoride or perfluoro-2, 5-dimethyl-3, 6-dioxanonanoyl fluoride for reaction at the temperature of 0 to-15 ℃; then separating and washing the organic solvent layer to obtain perfluoroacyl peroxide; in the two schemes, the titanium silicalite molecular sieve ionic liquid composite catalyst combines 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt ionic liquid with a titanium silicalite molecular sieve grafted by vinyl siloxane through hydrosilylation reaction; the preparation method comprises the following steps: according to the mass parts, under the nitrogen atmosphere, 30-40 parts of tetramethyldisilazane, 3-6 parts of 15% -20% isopropanol solution of chloroplatinic acid, 0.02-0.5 part of 1-vinyl-3-butylimidazole bistrifluoromethanesulfonylimide salt and 1000-2000 parts of isopropanol are added into a reaction kettle, uniformly stirred and mixed, then the 280 parts of vinylsiloxane grafted titanium-silicon molecular sieve of 120-plus type is added into the reaction kettle under stirring, stirred at 60-70 ℃ for 10-20h, then the temperature is controlled at 110-plus type and the isopropanol is evaporated at 120 ℃, the obtained solid is treated in an oven at 100-plus type and 150 ℃ for 1-3h, and the titanium-silicon molecular sieve ionic liquid composite catalyst is obtained.
2. A process for producing a perfluoroacyl peroxide according to claim 1, wherein said perfluoro or polyfluoro organic solvent is decafluoropentane, pentafluorodichloropropane, hexafluoropropylene dimer, hexafluoropropylene trimer, dichlorooctafluorobutane or perfluorotributylamine.
3. The method for preparing perfluoroacyl peroxide according to claim 1, wherein the mass ratio of the perfluoroalkoyl fluoride to the titanium silicalite ionic liquid composite catalyst is 1: 0.05-0.1.
4. The method for preparing perfluoroacyl peroxide according to claim 1, wherein the molar ratio of the perfluoroalkanoyl fluoride to the hydrogen peroxide is 2.00: 1.35-1.37.
5. The process for producing a perfluoroacyl peroxide according to claim 1, wherein said perfluoroalkanoyl fluoride is added to said system at a reaction temperature of-5 to-10 ℃.
6. A process for producing a perfluoroacyl peroxide according to claim 1, wherein said perfluoroalkylcoyl fluoride is perfluorocyclohexylacyl fluoride.
7. The method of claim 1, wherein the titanium silicalite ionic liquid composite catalyst uses a titanium silicalite modified by vinyltrimethoxysilane as a raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010875267.0A CN112079758B (en) | 2020-08-27 | 2020-08-27 | Preparation method of perfluoroalkyl acyl peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010875267.0A CN112079758B (en) | 2020-08-27 | 2020-08-27 | Preparation method of perfluoroalkyl acyl peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112079758A CN112079758A (en) | 2020-12-15 |
| CN112079758B true CN112079758B (en) | 2022-08-30 |
Family
ID=73728685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010875267.0A Active CN112079758B (en) | 2020-08-27 | 2020-08-27 | Preparation method of perfluoroalkyl acyl peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112079758B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651913B (en) * | 2021-09-10 | 2022-10-28 | 浙江巨化股份有限公司氟聚厂 | Preparation method of high-strength polytetrafluoroethylene resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003104966A (en) * | 2001-09-28 | 2003-04-09 | Nof Corp | Method for producing dialkyl peroxide |
| CN1660804A (en) * | 2004-12-29 | 2005-08-31 | 上海交通大学 | Omega peroxide of perfluorin-acyl sulfonyl halide and preparation method |
| CN101786977A (en) * | 2010-03-23 | 2010-07-28 | 浙江巨化股份有限公司 | Preparation method of perfluoroalkyl acyl superoxide |
| CN108658823A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | The method for preparing Peracetic acid |
| CN108794367A (en) * | 2017-05-04 | 2018-11-13 | 中国科学院上海有机化学研究所 | The preparation of perfluoroacyl peroxides |
| CN110143905A (en) * | 2018-02-13 | 2019-08-20 | 中国石油化工股份有限公司 | The method for preparing Perpropionic Acid |
-
2020
- 2020-08-27 CN CN202010875267.0A patent/CN112079758B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003104966A (en) * | 2001-09-28 | 2003-04-09 | Nof Corp | Method for producing dialkyl peroxide |
| CN1660804A (en) * | 2004-12-29 | 2005-08-31 | 上海交通大学 | Omega peroxide of perfluorin-acyl sulfonyl halide and preparation method |
| CN101786977A (en) * | 2010-03-23 | 2010-07-28 | 浙江巨化股份有限公司 | Preparation method of perfluoroalkyl acyl superoxide |
| CN108658823A (en) * | 2017-03-30 | 2018-10-16 | 中国石油化工股份有限公司 | The method for preparing Peracetic acid |
| CN108794367A (en) * | 2017-05-04 | 2018-11-13 | 中国科学院上海有机化学研究所 | The preparation of perfluoroacyl peroxides |
| CN110143905A (en) * | 2018-02-13 | 2019-08-20 | 中国石油化工股份有限公司 | The method for preparing Perpropionic Acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112079758A (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110790854B (en) | Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and preparation method thereof | |
| EP0427820A1 (en) | Process for preparing peroxidic perfluoropolyethers. | |
| JPH03184971A (en) | 4, 5-dichloro-2, 2, 4, 5-tetrafluoro-1, 3- dioxolane and its preparation | |
| EP2977410B1 (en) | Composition comprising polyether-based polymer and a nano-carbon material | |
| CN108440702B (en) | Preparation method of ethylene-tetrafluoroethylene copolymer with high thermal stability | |
| US2965595A (en) | Process for polymerizing tetrafluoroethylene in the presence of polymerstabilizing agents | |
| CN113166304B (en) | Method for producing fluorosulfonyl group-containing fluoropolymer, method for producing fluoropolymer containing salt-type sulfonic acid groups, and method for producing fluoropolymer containing acid-type sulfonic acid groups | |
| EP0124378B1 (en) | Fluorinated alkyl ether-containing ethylenes, precursors thereto, and copolymers thereof with tetrafluoroethylene | |
| EP0073069A1 (en) | Method of polymerizing vinyl ethers | |
| CN112079758B (en) | Preparation method of perfluoroalkyl acyl peroxide | |
| WO2016136951A1 (en) | Polyether-based polymer composition | |
| JP3806941B2 (en) | Method for producing fluoropolymer | |
| ITMI20010482A1 (en) | PERFLUORODIACILPEROSXI POLYMERIZATION INITIATORS | |
| CN101786977A (en) | Preparation method of perfluoroalkyl acyl superoxide | |
| JPH06345824A (en) | Production of fluorine-containing copolymer | |
| CN106117397B (en) | Fluorine-containing polymer concentrated dispersion liquid and method for preparing fluorine-containing polymer by using same | |
| JPS60168711A (en) | Manufacture of fluoride ion exchange polymer precursor | |
| JPS60156632A (en) | Manufacture of vinyl chloride ether monomer and intermediate | |
| RU2450023C1 (en) | Method of producing perfluorinated perfluoroethylene copolymer containing sulphonyl fluoride functional groups | |
| US4225404A (en) | Perfluoroolefin and perfluoroparaffin mixture and process for making same | |
| RU2109761C1 (en) | Method of producing tetrafluoroethylene copolymers with 12-15 mol % of hexafluoropropylene | |
| JPS5911582B2 (en) | Fluorinated acid fluoride and its manufacturing method | |
| US4859745A (en) | Stratified fibrous fluoropolymer compositions and process for forming such fluoropolymers | |
| CN108484815B (en) | Preparation method of ethylene-tetrafluoroethylene copolymer with high thermal stability | |
| RU2463312C1 (en) | Method of producing heat-treated tetrafluoroethylene and hexafluoropropylene copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |