A kind of fluorine-containing polyetheramine and preparation method thereof
By grafting ethylene oxide or propylene oxide under Lewis acid catalysis, combining the ammonization reaction of kettle reactor and multi-metal catalyst, the low conversion rate and molecular weight distribution of fluoropolyetheramine synthesis in traditional technology has been successfully solved. The wide problem has achieved efficient and economical preparation of fluoropolyetheramines.
Patent Information
- Application Number
- CN202410317394.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-20
- Publication Date
- 2024-12-24
- Estimated Expiration
- 2044-03-20
AI Technical Summary
The prior art is difficult to effectively synthesize fluoropolyether amines, especially because the fluorocarbon bond energy is large, traditional catalysts cannot effectively catalyze, have a wide molecular weight distribution, low conversion rate, and traditional ammonization methods cannot effectively produce fluoropolyether amines.
Using fluoroethanol or phenols as starting agents, ethylene oxide or propylene oxide is grafted under Lewis acid catalysis to produce fluoropolyether intermediates, and then ammonia is carried out through a kettle reactor and a multi-metal catalyst. The reaction was carried out to control the low temperature and medium pressure conditions to produce fluoropolyetheramine.
It achieves a narrow molecular weight distribution, high conversion rate, and a hydroxyl conversion rate of 99.0%. It has a simple process, economical and practical, and reduces production costs.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic synthesis, in particular to a fluorine-containing polyether amine and a preparation method thereof. Background Art
[0002] Organic fluorine polymer materials refer to polymer materials with a large number of fluorine atoms on the main chain or side chain carbon atoms, also known as fluorine-containing polymers. Due to their unique properties, organic fluorine polymers have been widely used in many industries and fields such as national defense, aerospace, machinery, chemical industry, medicine, and construction. In many high-tech fields, fluorine materials are irreplaceable key materials.
[0003] Polyetheramine, also known as amino-terminated polyether, is a class of polyoxyolefin compounds with a polyether backbone as the main molecular chain and amino-terminated at the end. Most of these amino-terminated polyethers use polyether as the reaction raw material. Through different treatment methods, the terminal hydroxyl group of the polyether polyol is converted into the corresponding amine group or amino group (the terminal group is usually a primary amino group, secondary amino group or polyamine group containing active hydrogen). Due to the reactivity of the terminal amino group or amine group at the end of the polyether backbone, it can react with a variety of reactive groups, such as epoxy groups and isocyanate groups; in addition, due to the presence of ether bonds in the polyether chain, it is easily soluble in a variety of organic matter, which greatly broadens the application scope of amino-terminated polyether in the industrial field. With its superior performance, amino-terminated polyether is widely used in the fields of synthetic raw materials for polyurethane (polyurea), curing agents for epoxy resins, and new generation gasoline detergents.
[0004] Patents CN 107849234 B and CN 201680040505.8 disclose a method for manufacturing (per)fluoropolyetheramines, which comprises reacting a sulfonic acid ester of a (per)fluoropolyether alcohol with an excess of ammonia or an organic amine at a specific temperature. The method allows (per)fluoropolyetheramines, especially primary, secondary and tertiary (per)fluoropolyetheramines, to be obtained in high yield and selectivity, and can be conveniently applied on an industrial scale. The above patents also point out that US 3810874 B, US 6984759 B, US5446205 B, JPH06219994, EP 0621298 A, EP 0665253 A, EP 1388556 A and other patents also have similar manufacturing methods.
[0005] Zhang Yingqiang et al. published "Research Progress of Fluorinated Polyether Polyols" in "Polymer Bulletin" and introduced that fluoropolyether polyols at home and abroad are mainly synthesized by the following processes: 1. ZDOL or similar ZDOL series fluoropolyether polyols synthesized using tetrafluoroethylene as raw material; 2. Hexafluoropropylene is grafted into polytetramethylene ether glycol (PTMG) chain to synthesize fluorinated PTMG; 3. Side chain fluoropolyether polyols are prepared by the ring-opening polymerization method of grafting fluorinated epoxy compounds.
[0006] However, due to the relatively large fluorine-carbon bond energy, the development of fluorinated alcohols grafted with EO / PO using fluorinated alcohol initiators has not been reported, and the synthesis of fluorinated polyether amines by hydroxy-catalyzed amination of fluorinated polyethers has not been reported either. Summary of the invention
[0007] In view of the problems existing in the prior art, the present invention provides a fluorinated polyetheramine and a preparation method thereof, which is simple, efficient, economical and practical. The product prepared by the present invention can be applied to the fields of self-cleaning coatings, anti-icing coatings, weather-resistant and aging-resistant epoxy resins, acid- and alkali-resistant polyurea elastomers, etc.
[0008] The present invention is achieved through the following technical solutions:
[0009] A fluorinated polyether amine is prepared by a special catalytic amination process using a fluorinated alcohol or phenolic substance as an initiator and a fluorinated polyether obtained by grafting ethylene oxide, propylene oxide or a mixture of the two under Lewis acid catalysis as an intermediate, and the fluorinated polyether amine has a structural formula of (1) or (2);
[0010]
[0011] Wherein, R is a hydrogen-containing group of a fluorine-containing initiator alcohol or phenol, m=0-10, n=0-10.
[0012] A method for preparing a fluorinated polyetheramine comprises the following steps:
[0013] (1) Add a certain amount of fluorinated alcohol or phenol initiator, ethylene glycol dimethyl ether and Lewis acid catalyst into a clean reactor, replace with nitrogen in vacuum for 3 times, slowly drop a certain amount of ethylene oxide, propylene oxide or a mixture of the two at 40-60°C and -0.10MPa, maintain the reaction pressure at 0.10-0.50MPa, and maintain the reaction temperature at 40-60°C. After the addition is completed, age at 70°C for 10 hours, then vacuum at 80°C and -0.10MPa for 2 hours to remove the solvent ethylene glycol dimethyl ether and small molecular substances, cool and discharge the material to obtain a fluorinated polyether intermediate;
[0014] (2) A quantitative amount of polyetheramine catalyst, fluorinated polyether intermediate, liquid ammonia and hydrogen are introduced into a clean intermittent reactor, stirring is started, the temperature is adjusted to 110-140°C, and the pressure is controlled to 2.50-3.50 MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 20-25 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained.
[0015] In the step (1), the molar ratio of the fluorinated alcohol or phenol initiator to ethylene oxide and propylene oxide is 1:0-10:0-10, the amount of ethylene glycol dimethyl ether is 3-6 times the mass of the fluorinated polyether intermediate, and the amount of the Lewis acid catalyst is 0.1-0.3% of the mass of the fluorinated polyether intermediate.
[0016] Preferably, the fluorine-containing alcohol or phenol initiator in step (1) is one or a mixture of tridecafluorooctanol, perfluorodecanol, hexafluorobisphenol A (bisphenol AF), and trifluorophenol.
[0017] Preferably, the Lewis acid catalyst in step (1) is one or a mixture of BF3, TiCl4, FeCl3, and AlCl3.
[0018] Preferably, in step (2), the molar ratio of the fluorinated polyether intermediate to liquid ammonia is 1:5-13, and the amount of the polyetheramine catalyst used is 0.2-0.5% of the mass of the fluorinated polyetheramine product.
[0019] Preferably, in the gas component in the reactor in step (2), the amount of hydrogen used is 10-20% of the volume of the hydrogen-ammonia mixed gas.
[0020] Preferably, the polyetheramine catalyst in step (2) is a reusable supported metal catalyst, comprising three parts: a multi-metal active component, an auxiliary agent and a carrier;
[0021] The multi-metal active component comprises, based on the total weight of the catalyst, 5-15 wt% of Pd, 5-20 wt% of Cu, 1-5 wt% of Co and 0.5-1.0 wt% of Ni;
[0022] The auxiliary agent is selected from one or more of Zr, Cr, Mo, Fe, Zn, Sn, Bi, and Ce, and the mass of the auxiliary agent is 1-5% of the total weight of the catalyst;
[0023] The carrier is a metal oxide, which is one or more of porous γ-Al2O3, MgO, TiO2 and ZrO2.
[0024] Preferably, the specific surface area of the polyetheramine catalyst in step (2) is 1000m 2 / g~1300m 2 / g, pore volume is 0.90cm 3 / g~1.25cm 3 / g, and the average pore size is 5nm~8nm.
[0025] Compared with the prior art, the present invention has the following beneficial effects:
[0026] 1. Due to the relatively large fluorine-carbon bond energy, the traditional alkali metal catalyst process cannot synthesize fluorinated polyethers. The fluorinated polyethers synthesized by traditional Lewis acid catalysts have a wide molecular weight distribution and a very low conversion rate. Compared with the prior art, the present invention synthesizes fluorinated polyether intermediates at low temperature in a large amount of alcohol ether solvents, and the molecular weight distribution is narrow, and the conversion rate of fluorinated polyethers is ≥98.0%;
[0027] 2. Since fluorinated polyethers are difficult to aminate, the mainstream continuous catalytic ammoniation method at home and abroad cannot synthesize fluorinated polyether amines; however, the present invention adopts a traditional kettle reactor and adopts low-temperature medium-pressure technology to effectively avoid high-temperature cracking of fluorinated polyethers. After reacting for 20 to 25 hours under the action of a specific catalyst, a fluorinated polyether amine product can be obtained, and the hydroxyl conversion rate is ≥99.0%. The present invention has a simple process, significant effect, and is economical and practical;
[0028] 3. In view of the low conversion rate of polyether grafted with ethylene oxide by nickel-based polyetheramine catalyst and the low hydroxyl conversion rate under low temperature conditions of kettle reactor, the present invention adopts multi-metal components with high palladium and high copper content and a supported catalyst with specific surface area and pore volume and pore size to solve the problem of low hydroxyl conversion rate in the amination process. Moreover, the catalyst used in the present invention can be recycled for more than 200 times, which greatly reduces the production cost. DETAILED DESCRIPTION
[0029] The present invention is further described below: Example
[0030] 1 mol of tridecafluorooctanol, 3 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.1% of BF3 of the mass of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced 3 times. 10 mol of propylene oxide was slowly added dropwise at 40°C and -0.10 MPa, and the reaction pressure and temperature were maintained at 0.10 MPa and 40°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0031] A multi-metal active component containing 5wt% Pd, 5wt% Cu, 1wt% Co and 0.5wt% Ni, an auxiliary component containing 1wt% Zr, and porous γ-Al2O3 as a carrier with a specific surface area of 1000m 2 / g, pore volume is 0.90cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 5nm.
[0032] 1 mol of fluorinated polyether intermediate, 0.2% of polyetheramine catalyst by mass of fluorinated polyetheramine, 5 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 10% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 110°C, and the pressure is controlled to 2.50MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 20 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0033] 1 mol of tridecafluorooctanol, 6 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.3% of the mass of TiCl4 of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced 3 times. 10 mol of ethylene oxide was slowly added dropwise at 60°C and -0.10 MPa, and the reaction pressure was maintained at 0.50 MPa and the reaction temperature was maintained at 60°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0034] A multi-metal active component containing 15wt% Pd, 20wt% Cu, 5wt% Co and 1wt% Ni, an auxiliary component containing 5wt% Cr, and porous MgO as a carrier with a specific surface area of 1300m 2 / g, pore volume is 1.25cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 8nm.
[0035] 1 mol of fluorinated polyether intermediate, 0.5% of polyetheramine catalyst by mass of fluorinated polyetheramine, 13 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 20% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 140°C, and the pressure is controlled to 3.50MPa. The raw materials react under the action of the catalyst in the reactor. After 25 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0036] 1 mol of perfluorodecanol, 4 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.2% of the mass of FeCl3 of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced 3 times. 3 mol of ethylene oxide was slowly added dropwise at 50°C and -0.10 MPa, and the reaction pressure was maintained at 0.20 MPa and the reaction temperature was maintained at 50°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0037] A multi-metal active component containing 9wt% Pd, 6wt% Cu, 1wt% Co and 0.6wt% Ni, an auxiliary component containing 1.5wt% Mo, and porous TiO2 as a carrier with a specific surface area of 1100m 2 / g, pore volume is 1.05cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 6nm.
[0038] 1 mol of fluorinated polyether intermediate, 0.3% of polyetheramine catalyst by mass of fluorinated polyetheramine, 6 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 12% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 120°C, and the pressure is controlled to 2.80MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 22 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0039] 1 mol of perfluorodecanol, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.2% of the mass of FeCl3 of the fluorinated polyether intermediate were added into a clean reactor in turn, and the vacuum nitrogen was replaced for 3 times. 5 mol of propylene oxide was slowly added dropwise at 50°C and -0.10 MPa, and the reaction pressure was maintained at 0.25 MPa and the reaction temperature was maintained at 50°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0040] A multi-metal active component containing 10wt% Pd, 8wt% Cu, 2wt% Co and 0.8wt% Ni, an auxiliary component containing 2wt% Fe, and porous ZrO2 as a carrier with a specific surface area of 1150m 2 / g, pore volume is 1.15cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 5nm.
[0041] 1 mol of fluorinated polyether intermediate, 0.4% of polyetheramine catalyst by mass of fluorinated polyetheramine, 8 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 13% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 125°C, and the pressure is controlled to 2.90MPa. The raw materials react under the action of the catalyst in the reactor. After 23 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0042] 1 mol of perfluorodecanol, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.25% of the mass of AlCl3 of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced 3 times. A mixture of 5 mol of propylene oxide and 3 mol of ethylene oxide was slowly added dropwise at 55°C and -0.10 MPa, and the reaction pressure was maintained at 0.45 MPa and the reaction temperature was maintained at 55°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0043] A multi-metal active component containing 11wt% Pd, 10wt% Cu, 3wt% Co and 0.9wt% Ni, an auxiliary component containing 3wt% Zn, and porous γ-Al2O3 as a carrier with a specific surface area of 1250m 2 / g, pore volume is 1.20cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 7nm.
[0044] 1 mol of fluorinated polyether intermediate, 0.5% of polyetheramine catalyst by mass of fluorinated polyetheramine, 11 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 15% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 135°C, and the pressure is controlled to 2.60MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 25 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0045] 1 mol of hexafluorobisphenol A, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.28% of the mass of TiCl4 of the fluorinated polyether intermediate were sequentially added into a clean reactor, and the vacuum nitrogen was replaced 3 times. A mixture of 10 mol of propylene oxide and 10 mol of ethylene oxide was slowly added dropwise at 58°C and -0.10 MPa, and the reaction pressure was maintained at 0.48 MPa and the reaction temperature was maintained at 58°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0046] A multi-metal active component containing 15wt% Pd, 8wt% Cu, 3wt% Co and 0.9wt% Ni, an auxiliary component containing 2wt% Bi, and porous MgO as a carrier with a specific surface area of 1180m 2 / g, pore volume is 1.25cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 8nm.
[0047] 1 mol of fluorinated polyether intermediate, 0.5% of polyetheramine catalyst by mass of fluorinated polyetheramine, 6 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 20% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 140°C, and the pressure is controlled to 3.40MPa. The raw materials react under the action of the catalyst in the reactor. After 25 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0048] 1 mol of hexafluorobisphenol A, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.28% of the mass of TiCl4 of the fluorinated polyether intermediate were sequentially added into a clean reactor, and the vacuum nitrogen was replaced 3 times. A mixture of 3 mol of propylene oxide and 8 mol of ethylene oxide was slowly added dropwise at 55°C and -0.10 MPa, and the reaction pressure was maintained at 0.48 MPa and the reaction temperature was maintained at 55°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and the material was discharged to obtain a fluorinated polyether intermediate.
[0049] A multi-metal active component containing 12wt% Pd, 8wt% Cu, 1wt% Co and 0.9wt% Ni, an auxiliary component containing 4wt% Sn, and porous γ-Al2O3 as a carrier with a specific surface area of 1280m 2 / g, pore volume is 1.22cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 7nm.
[0050] 1 mol of fluorinated polyether intermediate, 0.3% of polyetheramine catalyst by mass of fluorinated polyetheramine, 7 mol of liquid ammonia and hydrogen are introduced into a clean batch reactor, and the amount of hydrogen is controlled to be 16% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 130°C, and the pressure is controlled to 3.30MPa. The raw materials react under the action of the catalyst in the reactor. After 21 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0051] 1 mol of hexafluorobisphenol A, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.1% of the mass of TiCl4 of the fluorinated polyether intermediate were added into a clean reactor in turn, and the vacuum nitrogen was replaced for 3 times. 3 mol of propylene oxide was slowly added dropwise at 50°C and -0.10 MPa, and the reaction pressure was maintained at 0.18 MPa and the reaction temperature was maintained at 50°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0052] A multi-metal active component containing 6wt% Pd, 6wt% Cu, 2wt% Co and 0.5wt% Ni, an auxiliary component containing 3wt% Ce, and porous TiO2 as a carrier with a specific surface area of 1050m 2 / g, pore volume is 0.96cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 5nm.
[0053] 1 mol of fluorinated polyether intermediate, 0.25% of polyetheramine catalyst by mass of fluorinated polyetheramine, 6 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 11% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 115°C, and the pressure is controlled to 2.50MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 22 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0054] 1 mol of trifluorophenol, 5 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.2% of the mass of AlCl3 of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced 3 times. 5 mol of ethylene oxide was slowly added dropwise at 45°C and -0.10 MPa, and the reaction pressure was maintained at 0.28 MPa and the reaction temperature was maintained at 45°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecular substances, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0055] A multi-metal active component containing 11wt% Pd, 17wt% Cu, 2wt% Co and 0.8wt% Ni, an auxiliary component containing 2.5wt% Zr, and porous TiO2 as a carrier with a specific surface area of 1250m 2 / g, pore volume is 0.98cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 6nm.
[0056] 1 mol of fluorinated polyether intermediate, 0.25% of polyetheramine catalyst by mass of fluorinated polyetheramine, 6 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 12% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 125°C, and the pressure is controlled to 2.70MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 22 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0057] 0.3 mol of trifluorophenol, 0.7 mol of tridecafluorooctanol, 6 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.3% of the mass of AlCl3 of the fluorinated polyether intermediate were added into a clean reactor in turn, and the vacuum nitrogen was replaced 3 times. 8 mol of ethylene oxide was slowly added dropwise at 55°C and -0.10 MPa, and the reaction pressure was maintained at 0.48 MPa and the reaction temperature was maintained at 55°C. After the addition was completed, the reaction was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecules, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0058] A multi-metal active component containing 12wt% Pd, 15wt% Cu, 3wt% Co and 0.9wt% Ni, an auxiliary component containing 3.5wt% Zr, and porous TiO2 as a carrier with a specific surface area of 1290m 2 / g, pore volume is 1.15cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 6nm.
[0059] 1 mol of fluorinated polyether intermediate, 0.45% of polyetheramine catalyst by mass of fluorinated polyetheramine, 11 mol of liquid ammonia and hydrogen are introduced into a clean intermittent reactor, and the amount of hydrogen is controlled to be 15% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 138°C, and the pressure is controlled to 2.90MPa. The raw materials react under the action of the catalyst in the reactor. After 23 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained. Example
[0060] 0.5 mol of trifluorophenol, 0.5 mol of tridecafluorooctanol, 4 times the mass of ethylene glycol dimethyl ether of the fluorinated polyether intermediate, and 0.25% of the mass of AlCl3 of the fluorinated polyether intermediate were added into a clean reactor in sequence, and the vacuum nitrogen was replaced for 3 times. A mixture of 4 mol of ethylene oxide and 5 mol of propylene oxide was slowly added dropwise at 55°C and -0.10 MPa, and the reaction pressure was maintained at 0.38 MPa and the reaction temperature was maintained at 55°C. After the addition was completed, the reactor was aged at 70°C for 10 h, and then vacuumed at 80°C and -0.10 MPa for 2 h to remove the solvent ethylene glycol dimethyl ether and small molecules, and the temperature was lowered and discharged to obtain a fluorinated polyether intermediate.
[0061] The multi-metal active component containing 14wt% Pd, 5wt% Cu, 1wt% Co and 0.9wt% Ni, an auxiliary component containing 2.5wt% Cr, and porous ZrO2 as a carrier with a specific surface area of 1190m 2 / g, pore volume is 1.13cm 3 / g, a high palladium and high copper content polyetheramine catalyst with an average pore diameter of 7nm.
[0062] 1 mol of fluorinated polyether intermediate, 0.35% of polyetheramine catalyst by mass of fluorinated polyetheramine, 12 mol of liquid ammonia and hydrogen are introduced into a clean batch reactor, and the amount of hydrogen is controlled to be 17% of the volume of hydrogen-ammonia mixed gas. Stirring is started, the temperature is adjusted to 135°C, and the pressure is controlled to 3.30MPa. The raw materials react under the action of the catalyst in the reactor. After 25 hours of reaction, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained.
[0063] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the scope of implementation of the present invention. All equivalent changes and modifications to the shapes, structures, features and spirits described in the claims of the present invention should be included in the scope of the claims of the present invention.
Claims
1. A fluorinated polyetheramine, characterized in that: The fluorinated polyether amine is prepared by a special catalytic amination process using fluorinated alcohols or phenols as initiators, grafting ethylene oxide, propylene oxide or a mixture of the two as intermediates under Lewis acid catalysis, and has the structural formula (1) or (2). Wherein, R is a hydrogen-containing group of a fluorinated initiator alcohol or phenol, m=1-10, n=1-10; The preparation method of the fluorinated polyether amine comprises the following steps: (1) Add a certain amount of fluorinated alcohol or phenol initiator, ethylene glycol dimethyl ether and Lewis acid catalyst into a clean reactor, replace with nitrogen in vacuum for 3 times, slowly drop a certain amount of ethylene oxide, propylene oxide or a mixture of the two at 40-60°C and -0.10MPa, maintain the reaction pressure at 0.10-0.50MPa, and maintain the reaction temperature at 40-60°C. After the addition is completed, age at 70°C for 10 hours, then vacuum at 80°C and -0.10MPa for 2 hours to remove the solvent ethylene glycol dimethyl ether and small molecular substances, cool and discharge the material to obtain a fluorinated polyether intermediate; (2) A quantitative amount of polyetheramine catalyst, fluorinated polyether intermediate, liquid ammonia and hydrogen are introduced into a clean intermittent reactor, stirring is started, the temperature is adjusted to 110-140°C, and the pressure is controlled to 2.50-3.50 MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 20-25 hours, the temperature is lowered to 100°C, ammonia, hydrogen and water are removed under reduced pressure, and the catalyst is cooled and filtered to obtain a fluorinated polyetheramine finished product; In the step (1), the molar ratio of the fluorinated alcohol or phenol initiator to ethylene oxide and propylene oxide is 1:0-10:0-10, wherein the molar amounts of ethylene oxide and propylene oxide are not 0 at the same time, the amount of ethylene glycol dimethyl ether is 3-6 times the mass of the fluorinated polyether intermediate, and the amount of the Lewis acid catalyst is 0.1-0.3% of the mass of the fluorinated polyether intermediate; In the step (2), the molar ratio of the fluorinated polyether intermediate to liquid ammonia is 1:5-13, and the amount of the polyetheramine catalyst used is 0.2-0.5% of the mass of the fluorinated polyetheramine product; The polyetheramine catalyst in step (2) is a reusable supported metal catalyst, comprising three parts: a multi-metal active component, an auxiliary agent and a carrier; The multi-metal active component comprises, based on the total weight of the catalyst, 5-15 wt% of Pd, 5-20 wt% of Cu, 1-5 wt% of Co and 0.5-1.0 wt% of Ni; The auxiliary agent is selected from one or more of Zr, Cr, Mo, Fe, Zn, Sn, Bi, and Ce, and the mass of the auxiliary agent is 1-5% of the total weight of the catalyst; The carrier is a metal oxide, which is porous γ-Al2O3, MgO, TiO2 and ZrO2 in one or more; The specific surface area of the polyetheramine catalyst in step (2) is 1000 m 2 / g~1300m 2 / g, pore volume is 0.90cm 3 / g~1.25cm 3 / g, and the average pore size is 5nm~8nm.
2. The method for preparing a fluorinated polyetheramine according to claim 1, characterized in that: The steps include: (1) Add a certain amount of fluorinated alcohol or phenol initiator, ethylene glycol dimethyl ether and Lewis acid catalyst into a clean reactor, replace with nitrogen in vacuum for 3 times, slowly drop a certain amount of ethylene oxide, propylene oxide or a mixture of the two at 40-60°C and -0.10MPa, maintain the reaction pressure at 0.10-0.50MPa, and maintain the reaction temperature at 40-60°C. After the addition is completed, age at 70°C for 10 hours, then vacuum at 80°C and -0.10MPa for 2 hours to remove the solvent ethylene glycol dimethyl ether and small molecular substances, cool and discharge the material to obtain a fluorinated polyether intermediate; (2) A quantitative amount of polyetheramine catalyst, fluorinated polyether intermediate, liquid ammonia and hydrogen are introduced into a clean intermittent reactor, stirring is started, the temperature is adjusted to 110-140°C, and the pressure is controlled to 2.50-3.50 MPa. The raw materials react under the action of the catalyst in the reactor. After reacting for 20-25 hours, the temperature is lowered to 100°C, and ammonia, hydrogen and water are removed under reduced pressure. After cooling and filtering the catalyst, the fluorinated polyetheramine product is obtained.
3. A fluorinated polyetheramine and a preparation method thereof according to claim 2, characterized in that: In the step (1), the fluorine-containing alcohol or phenol initiator is one of tridecafluorooctanol, perfluorodecanol, hexafluorobisphenol A (bisphenol AF), trifluorophenol or a mixture thereof.
4. A fluorinated polyetheramine and a preparation method thereof according to claim 2, characterized in that: The Lewis acid catalyst in step (1) is one or a mixture of BF3, TiCl4, FeCl3, and AlCl3.
5. A fluorinated polyetheramine and a preparation method thereof according to claim 2, characterized in that: In the gas component in the reactor in step (2), the amount of hydrogen used is 10-20% of the volume of the hydrogen-ammonia mixed gas.