Isomerization reaction catalyst of perfluoro-4-methyl-2-pentene
Low conversion and selectivity were solved by using a main catalyst and cocatalyst in the isomerization reaction of perfluoro-4-methyl-2-pentene, combining an impregnated solution with aprotic polar solvent and specific molecular sieves. The problem of this problem has achieved efficient isomerization reactions and improved the potential for industrial application.
Patent Information
- Application Number
- CN202310251461.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-03-16
- Publication Date
- 2024-12-17
- Estimated Expiration
- 2043-03-16
AI Technical Summary
The conversion rate and low selectivity of perfluoro-4-methyl-2-pentene are not high in isomerization reaction, which limits its industrial application.
The method of synergistic catalysis of the main catalyst and the cocatalyst is used to prepare the isomerization reaction by adding aprotic polar solvent and perfluoro-4-methyl-2-pentene into the reactor, and a specific molecular sieve and impregnation solution are used to prepare the auxiliary. Catalyst, improve reaction efficiency and conversion rate.
It significantly improves the conversion rate of perfluoro-4-methyl-2-pentene, saves raw materials, reduces costs, and effectively saves reaction time, and improves the efficiency of catalytic isomerization reaction.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic fluorine chemical industry, in particular to an isomerization reaction catalyst of perfluoro-4-methyl-2-pentene. Background Art
[0002] Hexafluoropropylene dimer has two structures: perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene. Hexafluoropropylene oligomers have good thermal and chemical stability and are very important chemical raw materials, which can be used to derive many fluorinated surfactants.
[0003] Application No. CN202210586403.3 applies for a system and method for continuous synthesis of perfluoro-4-methyl-2-pentene, the system comprising a reactor, a phase separation tank, a heat exchanger, an ejector and a flash tank, wherein the phase separation tank is connected in parallel with the heat exchanger, and the inlets are connected to the reactor outlet, the outlet of the heat exchanger is connected to the fast fluid inlet of the ejector, and the ejector outlet is connected to the reactor; the top outlet of the phase separation tank is connected to the reactor, and the bottom outlet is connected to the flash tank; the top outlet of the flash tank is connected to the ejector.
[0004] Publication No. CN107473929A discloses a method for co-producing perfluoro-2-methyl-2-pentene and perfluoro-4-methyl-2-pentene, including a recycling process. It has the characteristics of high conversion rate and selectivity, mild and controllable reaction conditions, catalyst and solvent can be recycled in the reactor, and separation of reaction products is simple.
[0005] In view of the above-mentioned patent disclosure and prior art, the applicant believes that the isomerization reaction of perfluoro-4-methyl-2-pentene to prepare perfluoro-2-methyl-2-pentene has the current status of low conversion rate and low selectivity, which limits its industrial application. Summary of the invention
[0006] The present invention provides a catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene to solve at least one technical problem raised in the above-mentioned background technology, and belongs to the technical field of organic fluorine chemical industry.
[0007] In order to achieve the purpose of the invention, the technical solution adopted by the present invention is:
[0008] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0009] According to the mass percentage, 30-60 parts of aprotic polar solvent are added into the reaction kettle, and then 200-400 parts of perfluoro-4-methyl-2-pentene are added, and a catalytic isomerization reaction is carried out under the action of a catalyst to obtain perfluoro-2-methyl-2-pentene.
[0010] In the present invention, the aprotic polar solvent is at least one of acetonitrile, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and cyclopentane sulfone.
[0011] In the present invention, the reaction temperature is 40-160° C., the reaction time is 5-25 h, and the reaction pressure is 0.1-1.0 MPa.
[0012] In the present invention, the catalysis is a coordinated catalysis of a main catalyst and a co-catalyst.
[0013] In the present invention, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:0.2-6:10-60; the molar ratio of the main catalyst to the raw material is 0.01-0.25.
[0014] In the present invention, the main catalyst is tetra(N,N-dialkylamino)ethylene, cyanide, cyanate, thiocyanate, alkali metal fluoride, alkaline earth metal fluoride, aluminum chlorofluoride, Lewis acid or a mixture thereof.
[0015] In the present invention, the preparation method of the co-catalyst is:
[0016] According to the mass fraction, 100-200 parts of molecular sieves are immersed in 1500-1620 parts of the impregnation solution, and the temperature is raised and stirred to react for a certain period of time. After the reaction is completed, the mixture is filtered and dried to obtain a promoter.
[0017] In the present invention, the molecular sieve includes one or more of ZSM type, Y type, β type, MCM type, SAPO type, and mordenite.
[0018] In the present invention, the impregnation solution contains 2-5 parts of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 0.02-0.5 parts of porphyrin manganese complex and 3-7 parts of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 10-17 parts of aluminum acrylate, 50-70 parts of diethylamine, and the remaining component is N,N-dimethylformamide.
[0019] In the present invention, the reaction temperature during the preparation of the co-catalyst is 40-50°C and the reaction time is 10-20h.
[0020] Reaction mechanism: In the present invention, the 2-aminomethyl-15-crown-5 and acrylic-cage polysilsesquioxane undergo amino addition reaction, and aluminum acrylate and diethylamine undergo amino addition reaction, and then they are compounded with the porphyrin manganese complex to obtain the active component of the co-catalyst.
[0021] Compared with the prior art, the present invention has the following beneficial effects:
[0022] (1) In this method, a main catalyst and a co-catalyst are combined to catalyze the isomerization reaction, thereby improving the conversion rate of perfluoro-4-methyl-2-pentene, saving raw materials and reducing costs.
[0023] (2) The active components of the co-catalyst in this method effectively improve the efficiency of the catalytic isomerization reaction and save reaction time. DETAILED DESCRIPTION
[0024] The present invention is further described below in conjunction with specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all possible alternatives, improvements and equivalents within the scope of the claims.
[0025] <Example 1>
[0026] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0027] 30 g of aprotic polar solvent was added into the reaction kettle, and then 200 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0028] In this example, the aprotic polar solvent is acetonitrile.
[0029] In this example, the reaction temperature is 40° C., the reaction time is 25 h, and the reaction pressure is 1.0 MPa.
[0030] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0031] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:0.2:10; the molar ratio of the main catalyst to the raw material is 0.12.
[0032] In this example, the main catalyst is tetra(N,N-dialkylamino)ethylene.
[0033] In this example, the preparation method of the co-catalyst is:
[0034] Immerse 100g of molecular sieve into 1500g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a co-catalyst.
[0035] In this example, the molecular sieve is ZSM-5 molecular sieve.
[0036] In this example, the impregnation solution contains 2 g of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 0.02 g of porphyrin manganese complex and 3 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 10 g of aluminum acrylate, 50 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0037] In this example, the reaction temperature during the preparation of the co-catalyst is 40° C. and the reaction time is 20 h.
[0038] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 98.2%.
[0039] <Example 2>
[0040] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0041] 40 g of aprotic polar solvent was added into the reaction kettle, and then 250 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0042] In this example, the aprotic polar solvent is N,N-dimethylacetamide.
[0043] In this example, the reaction temperature is 75° C., the reaction time is 20 h, and the reaction pressure is 0.8 MPa.
[0044] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0045] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:1.2:24; and the molar ratio of the main catalyst to the raw material is 0.14.
[0046] In this example, potassium cyanide is used as the main catalyst.
[0047] In this example, the preparation method of the co-catalyst is:
[0048] Immerse 120g of molecular sieve into 1540g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a co-catalyst.
[0049] In this example, the molecular sieve is β molecular sieve.
[0050] In this example, the impregnation solution contains 3 g of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 0.24 g of porphyrin manganese complex and 4 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 12 g of aluminum acrylate, 55 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0051] In this example, the reaction temperature during the preparation of the co-catalyst was 42° C. and the reaction time was 18 h.
[0052] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 98.9%.
[0053] <Example 3>
[0054] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0055] 50 g of aprotic polar solvent was added into the reaction kettle, and then 350 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0056] In this example, the aprotic polar solvent is dimethyl sulfoxide.
[0057] In this example, the reaction temperature is 125° C., the reaction time is 10 h, and the reaction pressure is 0.5 MPa.
[0058] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0059] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:4.8:35; the molar ratio of the main catalyst to the raw material is 0.19.
[0060] In this example, potassium thiocyanate is selected as the main catalyst.
[0061] In this example, the preparation method of the co-catalyst is:
[0062] Immerse 160g of molecular sieve into 1600g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a promoter.
[0063] In this example, the molecular sieve is MCM-41 molecular sieve.
[0064] In this example, the impregnation solution contains 4 g of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 0.43 g of porphyrin manganese complex and 5 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 14 g of aluminum acrylate, 65 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0065] In this example, the reaction temperature during the preparation of the co-catalyst was 45° C. and the reaction time was 15 h.
[0066] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 99.4%.
[0067] <Example 4>
[0068] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0069] 60 g of aprotic polar solvent was added into the reaction kettle, and then 400 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0070] In this example, the aprotic polar solvent is sulfolane.
[0071] In this example, the reaction temperature is 160° C., the reaction time is 5 h, and the reaction pressure is 0.2 MPa.
[0072] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0073] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:6:60; and the molar ratio of the main catalyst to the raw material is 0.25.
[0074] In this example, the main catalyst is antimony pentafluoride.
[0075] In this example, the preparation method of the co-catalyst is:
[0076] Immerse 200g of molecular sieve into 1620g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a promoter.
[0077] In this example, the molecular sieve is SAPO-34 molecular sieve.
[0078] In this example, the impregnation solution contains 5 g of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 0.5 g of porphyrin manganese complex and 7 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 17 g of aluminum acrylate, 70 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0079] In this example, the reaction temperature during the preparation of the co-catalyst was 50° C. and the reaction time was 10 h.
[0080] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 99.8%.
[0081] <Comparative Example 1>
[0082] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0083] 30 g of aprotic polar solvent was added into the reaction kettle, and then 200 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0084] In this example, the aprotic polar solvent is acetonitrile.
[0085] In this example, the reaction temperature is 40° C., the reaction time is 25 h, and the reaction pressure is 1.0 MPa.
[0086] In this example, the catalyst is tetra(N,N-dialkylamino)ethylene, and the molar ratio of catalyst to raw material is 0.12.
[0087] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 85.2%.
[0088] <Comparative Example 2>
[0089] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0090] 30 g of aprotic polar solvent was added into the reaction kettle, and then 200 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0091] In this example, the aprotic polar solvent is acetonitrile.
[0092] In this example, the reaction temperature is 40° C., the reaction time is 25 h, and the reaction pressure is 1.0 MPa.
[0093] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0094] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:0.2:10; the molar ratio of the main catalyst to the raw material is 0.12.
[0095] In this example, the main catalyst is tetra(N,N-dialkylamino)ethylene.
[0096] In this example, the preparation method of the co-catalyst is:
[0097] Immerse 100g of molecular sieve into 1500g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a co-catalyst.
[0098] In this example, the molecular sieve is ZSM-5 molecular sieve.
[0099] In this example, the impregnation solution contains 0.02 g of porphyrin manganese complex and 3 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 10 g of aluminum acrylate, 50 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0100] In this example, the reaction temperature during the preparation of the co-catalyst is 40° C. and the reaction time is 20 h.
[0101] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 93.1%.
[0102] <Comparative Example 3>
[0103] A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, comprising the following steps:
[0104] 30 g of aprotic polar solvent was added into the reaction kettle, and then 200 g of perfluoro-4-methyl-2-pentene was added, and a catalytic isomerization reaction was carried out under the action of the catalyst to obtain perfluoro-2-methyl-2-pentene.
[0105] In this example, the aprotic polar solvent is acetonitrile.
[0106] In this example, the reaction temperature is 40° C., the reaction time is 25 h, and the reaction pressure is 1.0 MPa.
[0107] In this example, the catalysis is a coordinated catalysis between a main catalyst and a co-catalyst.
[0108] In this example, the mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:0.2:10; the molar ratio of the main catalyst to the raw material is 0.12.
[0109] In this example, the main catalyst is tetra(N,N-dialkylamino)ethylene.
[0110] In this example, the preparation method of the co-catalyst is:
[0111] Immerse 100g of molecular sieve into 1500g of impregnation solution, heat and stir to react for a certain period of time, and after the reaction is completed, filter and dry to obtain a co-catalyst.
[0112] In this example, the molecular sieve is ZSM-5 molecular sieve.
[0113] In this example, the impregnation solution contains 2 g of 2-aminomethyl-15-crown-5, CAS: 83585-56-2, 3 g of acrylic-cage polysilsesquioxane, CAS: 1620202-27-8, 10 g of aluminum acrylate, 50 g of diethylamine, and the remaining component is N,N-dimethylformamide.
[0114] In this example, the reaction temperature during the preparation of the co-catalyst is 40° C. and the reaction time is 20 h.
[0115] After separation and purification, analysis revealed that perfluoro-4-methyl-2-pentene had been converted into perfluoro-2-methyl-2-pentene, and the conversion rate of the reaction was 94.8%.
[0116] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.
Claims
1. A catalyst for the isomerization reaction of perfluoro-4-methyl-2-pentene, Features: The steps include: Add 30-60 parts by mass of a non-protonic polar solvent into a reaction kettle, and then add 200-400 parts of perfluoro-4-methyl-2-pentene, and carry out catalytic isomerization reaction under the action of a catalyst to obtain perfluoro-2-methyl-2-pentene; The catalysis is carried out by a main catalyst and a co-catalyst in a coordinated manner; The preparation method of the co-catalyst is: According to the mass fraction, 100-200 parts of molecular sieve are immersed in 1500-1620 parts of impregnation solution, heated and stirred for reaction for a certain period of time, and after the reaction is completed, filtered and dried to obtain a promoter; The impregnation solution contains 2-5 parts of 2-aminomethyl-15-crown-5, 0.02-0.5 parts of porphyrin manganese complex, 3-7 parts of acrylic-cage polysilsesquioxane, 10-17 parts of aluminum acrylate, 50-70 parts of diethylamine, and the remaining component is N,N-dimethylformamide; The main catalyst is tetra(N,N-dialkylamino)ethylene, cyanide, cyanate, thiocyanate, alkali metal fluoride, alkaline earth metal fluoride, Lewis acid or a mixture thereof.
2. The isomerization reaction catalyst of perfluoro-4-methyl-2-pentene according to claim 1, Features: The aprotic polar solvent is at least one of acetonitrile, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and cyclopentane sulfone.
3. The isomerization reaction catalyst of perfluoro-4-methyl-2-pentene according to claim 1, It is characterized in that The catalytic isomerization reaction temperature is 40-160° C., the reaction time is 5-25 h, and the reaction pressure is 0.1-1.0 MPa.
4. The isomerization reaction catalyst of perfluoro-4-methyl-2-pentene according to claim 1, Features: The mass ratio of the main catalyst, the co-catalyst and the aprotic polar solvent is 1:0.2-6:10-60; the molar ratio of the main catalyst to perfluoro-4-methyl-2-pentene is 0.01-0.
25.
5. The isomerization reaction catalyst of perfluoro-4-methyl-2-pentene according to claim 1, Features: The molecular sieve includes one or more of ZSM type, Y type, β type, MCM type, SAPO type, and mordenite.
6. The isomerization reaction catalyst of perfluoro-4-methyl-2-pentene according to claim 1, Features: The reaction temperature during the preparation of the co-catalyst is 40-50°C and the reaction time is 10-20h.