CN114395117A - Double-end perfluoropolyether and preparation method thereof - Google Patents
Double-end perfluoropolyether and preparation method thereof Download PDFInfo
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Abstract
The invention discloses double-end perfluoropolyether and a preparation method thereof. The structural formula of the disclosed double-end perfluoropolyether is shown as a formula (I); the preparation method mainly comprises the steps of in the presence of metal fluoride, fluorinating N, N-bis (perfluoroalkyl acyloxy alkyl) amine or bis (perfluoroalkyl acyloxy alkyl) alkylamine by an active fluorine source to obtain a dihydric alcohol amine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by irradiating a fluorinating reagent with ultraviolet light, wherein the fluorinating reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas; then under the irradiation of ultraviolet light, carrying out photo-oxidation polymerization on the perfluoroolefin monomer, the second fluorine-containing olefin monomer, the glycol amine fluoride and oxygen to obtain a diacyl end-group polymer; then, the diacyl-terminated polymer is fluorinated by adopting an active fluorine source at the temperature of between 50 and 120 ℃ to obtain the double-ended perfluoropolyether. The method is mainly used for preparing the double-end perfluoropolyether containing nitrogen atoms in the main chain structure.
Description
Technical Field
The invention belongs to the technical field of perfluoropolyether, and particularly relates to double-end perfluoropolyether prepared by carrying out photo-oxidative polymerization on a mixed gas of perfluoroolefin, fluoroolefin, dialkanolamine fluoride and oxygen and carbon dioxide and a preparation method thereof.
Background
Perfluoropolyether is a polymer compound produced by substituting hydrogen in an alkane with fluorine, oxygen, or the like, and contains only C, F, O elements in the molecule. Due to strong electronegativity and pseudo-effect of fluorine atoms and shielding effect of C-F bonds on main chain C-C bonds, the perfluoropolyether generally has low condensation point, high viscosity index and excellent high temperature resistance, corrosion resistance, radiation resistance and chemical stability, and is widely applied to the fields of electronics, electrical engineering, chemical machinery, aerospace, nuclear industry and the like.
At present, there are two main methods for preparing perfluoropolyether. The first is anion polymerization represented by hexafluoropropylene oxide, although the method has simple process, safe and controllable process and high reaction yield, the prepared perfluoropolyether has small molecular weight which is generally between 1000 and 7000, and low viscosity index (less than 150), and is difficult to meet the use requirements of lubrication and sealing under severe conditions such as wide temperature range and the like. The second is the preparation of perfluoropolyether by the oxidative polymerization of perfluoroolefin, which usually adopts a tank reactor or a photochemical reactor, takes perfluoroolefin and oxygen as raw materials, and obtains stable perfluoropolyether by the initiation polymerization of chemical initiator or ultraviolet light and the fluorination treatment. The process for preparing perfluoropolyethers by chemical initiators is generally extremely difficult to control, the resulting perfluoropolyether products have low molecular weights and it is difficult to obtain products having high degrees of polymerization, as disclosed in US5258110 as F2As an initiator, a compound selected from the group consisting of,the molecular weight of the peroxide perfluoropolyether obtained by the reaction of tetrafluoroethylene and oxygen in a solvent is only about 3000 at most. CN1167124A discloses the use of COF in the presence of chemical initiators containing at least one F-X bond2The oxidative polymerization of tetrafluoroethylene is carried out in a solvent with a molar content higher than 8%, the reaction pressure is controlled to be 0-15 bar, perfluoropolyether with a PO value (PO value is the mass of active oxygen contained in each 100g of compound) less than 4 is obtained, and the number average molecular weight of the perfluoropolyether is still less than 10000 although the number average molecular weight is improved. US10029981 discloses a process for the preparation of perfluoropolyether acid fluorides by reacting perfluoroolefins with oxygen in a microreactor under ultraviolet irradiation, with overall yields below 40%, although the reaction allows to obtain products with average molecular weights between 5000 and 20000. U.S. Pat. nos. US4451646, US3715378, and US3847978 disclose methods for preparing perfluoropolyether by photocatalytic oxidative polymerization, which are generally radical reaction mechanisms, and involve addition of oxygen and central radical, perfluoroperoxy radical chain growth, perfluoroalkoxy chain growth, perfluoroperoxy radical degradation to generate perfluoroalkoxy radical, perfluoroperoxy radical coupling chain termination reaction, and the like, and have complex process and high technical difficulty, and also require continuous improvement and optimization to realize efficient and safe preparation of high molecular weight perfluoropolyether. In addition, with the continuous development and expansion of the use of the perfluoropolyether compound, new requirements are also put forward on the molecular weight and the structure of the perfluoropolyether, and the modification and the regulation of the main chain structure of the perfluoropolyether are particularly important when the perfluoropolyether is prepared.
Disclosure of Invention
Aiming at the defects or shortcomings of the prior art, the invention provides double-end perfluoropolyether.
The structural formula of the double-end perfluoropolyether provided by the invention is shown as the formula (I):
wherein, the first and second connecting parts are connected with each other; x is F, CF3-，C2F5Or C3F7(ii) a A is CF3-or C2F5-; b is CF3-or C2F5-; a1, a2, b1, b2, c1 and c2 are all greater than or equal to 1; n is 0, 1 or 2; the average molecular weight of the double-end perfluoropolyether is 4000-30000 Da.
Meanwhile, the invention provides a preparation method of the double-end perfluoropolyether. The preparation method comprises the following steps:
(1) in the presence of metal fluoride, N, N-bis (perfluoroalkyl acyloxy alkyl) amine or bis (perfluoroalkyl acyloxy alkyl) alkylamine is fluorinated by an active fluorine source to obtain a dialkanolamine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by irradiating a fluorinating reagent with ultraviolet light, wherein the fluorinating reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas;
(2) under the irradiation of ultraviolet light, carrying out photooxidation polymerization on a perfluoroolefin monomer, a second fluorine-containing olefin monomer, a binary alcohol amine fluoride and oxygen or oxygen carbon dioxide mixed gas to obtain a diacyl-terminated polymer; the photo-oxidative polymerization reaction conditions are as follows: the reaction temperature is-70 ℃ to-25 ℃, and the reaction pressure is 0.5bar to 4 bar; the second fluorine-containing olefin monomer is a C2-C4 fluorine-containing olefin;
(3) and (3) carrying out fluorination treatment on the diacyl-terminated polymer at the temperature of between 50 and 120 ℃ by adopting an active fluorine source to obtain the double-ended perfluoropolyether.
Optionally, the N, N-bis (perfluoroalkanoyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (pentafluoropropionyloxybutyl) amine, N-bis (trifluoroacetyloxyethyl) amine, N-bis (trifluoroacetyloxypropyl) amine or N, N-bis (trifluoroacetyloxybutyl) amine; the bis (perfluoroalkanoyloxyalkyl) alkylamine is selected from bis (pentafluoropropionyloxyethyl) methylamine, bis (pentafluoropropionyloxyethyl) ethylamine, bis (pentafluoropropionyloxyethyl) propylamine, bis (trifluoroacetyloxyethyl) methylamine, bis (trifluoroacetyloxyethyl) ethylamine, bis (trifluoroacetyloxyethyl) propylamine, bis (pentafluoropropionyloxypropyl) methylamine, bis (pentafluoropropionyloxypropyl) ethylamine, bis (trifluoroacetyloxypropyl) methylamine, bis (trifluoroacetyloxypropyl) ethylamine, bis (pentafluoropropionyloxybutyl) methylamine, bis (pentafluoropropionyloxybutyl) ethylamine, bis (trifluoroacetyloxybutyl) methylamine or bis (trifluoroacetyloxybutyl) ethylamine.
Optionally, the perfluoroolefin monomer is one or more selected from tetrafluoroethylene, hexafluoropropylene and hexafluorobutadiene.
Optionally, the second fluoroolefin monomer is selected from vinylidene fluoride, trifluoroethylene, 3,3, 3-trifluoropropene, 2,3,3, 3-tetrafluoropropene, 1,1,1,2, 3-pentafluoropropene, 1,1,1,3, 3-pentafluoropropene, 1,1,1,4,4, 4-hexafluoro-2-butene, 1-chloro-3, 3, 3-trifluoropropene, 2-chloro-3, 3, 3-trifluoropropene, 1, 2-dichloro-3, 3, 3-trifluoropropene, 1-chloro-2, 3,3, 3-tetrafluoropropene, or 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene.
Optionally, the volume ratio of oxygen to carbon dioxide in the oxygen-carbon dioxide mixed gas is 7-10: 0-3.
Optionally, the reaction temperature of the photo-oxidative polymerization reaction is-60 ℃ to-40 ℃.
Optionally, the molar amount of the dialkanolamine fluoride to the total molar amount of the monomers is 1: 50 to 350.
The method further comprises the step of performing fraction segmentation on the obtained double-ended perfluoropolyether by molecular distillation to obtain the double-ended perfluoropolyethers with different average molecular weights.
The invention realizes the modification and regulation of the main chain structure of the perfluoropolyether, synthesizes a series of novel double-end perfluoropolyethers with nitrogen atoms on the main chain, and provides a new thought for the modification of the perfluoropolyethers. The preparation method of the double-end perfluoropolyether has the characteristics of high catalytic activity, safe and controllable reaction process and high yield.
Detailed Description
Unless otherwise specified, the terms herein are understood or implemented using established methods of correlation, as recognized by one of ordinary skill in the relevant art.
Based on the disclosure of the present invention, a person skilled in the art can optimize and select related parameters such as the relation of the amount of the substance, the reaction temperature, the reaction duration, the atmosphere composition and the amount of the gas introduced in the present invention, and the optimized and selected solution is not limited to the specific range and examples disclosed in the present invention. The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The average molecular weights of the two-terminal perfluoropolyethers in the following examples were determined using a Bruker 500MHz NMR spectrometer19F-NMR test analysis is carried out; the viscosity of the double-ended perfluoropolyether was measured using a viscometer model MCR302, austria antopa ltd, under the following test conditions: the temperature rise rate is 5 ℃/min, the test temperature range is 20-120 ℃, and the viscosity index of the sample is calculated by adopting the national standard GB/T1995-; the pour point of the perfluoropolyether is determined by the national standard GB/T3535-2006.
Example 1
Adding 400mL of N, N-bis (pentafluoropropionyloxyethyl) amine 25.0g (62.5mmol), cesium fluoride 1.5g (10.0mmol) and 1,2, 2-trifluoro-1, 1, 2-trichloroethane into a 1.25L photocatalytic reaction kettle equipped with a mechanical stirring and a condenser, replacing with high-purity nitrogen for two times, starting stirring, introducing an active fluorine gas mixed gas at 50mL/min at room temperature for reaction for 12h with a reaction pressure of 2bar, heating to 80 ℃, violently stirring for 9h, controlling the temperature of the condenser at about 30 ℃, reducing the temperature of the reaction system to-30 ℃, then adding 550mL of 1,2, 2-trifluoro-1, 1, 2-trichloroethane, introducing an oxygen and carbon dioxide mixed gas (the flow ratio of oxygen to carbon dioxide is 8:2), starting an LED ultraviolet lamp (wavelength 254nm) with the power of 200W, then tetrafluoroethylene and 2-chloro-3, 3, 3-trifluoropropene are introduced according to a certain proportion, the molar ratio of oxygen to tetrafluoroethylene to 2-chloro-3, 3, 3-trifluoropropene is controlled to be 2.5:0.7:0.3 during the reaction, the reaction pressure is 1bar, the ultraviolet lamp is kept to irradiate for 20 hours, then the ultraviolet lamp is closed, the introduction of fluoroolefin monomers is stopped, the mixed gas of oxygen and carbon dioxide is continuously introduced for 30 minutes and then stopped, the reaction temperature is gradually increased to the room temperature, unreacted perfluoroolefin and fluoroolefin monomers are condensed and recovered, the effective input amount of fluoroolefin monomers is about 15mol, the polymer with diacyl end groups is prepared, finally the ultraviolet lamp is opened, the mixed gas of active fluorine gas is adopted for fluorination treatment, the temperature is 100 ℃, and the time is 100 DEG C15h to obtain the double-end perfluoropolyether19F-NMR nuclear magnetic resonance spectroscopy analysis shows that the average molecular weight is about 18000Da, weighing is carried out, and the calculated yield is about 75 percent based on the input of the fluoroolefin monomer.
The preparation method of the active fluorine gas mixture comprises the following steps: vacuumizing a 1L stainless steel photocatalytic reaction kettle with a light source cold trap, replacing nitrogen for three times, introducing 30% fluorine gas/nitrogen mixed gas (V/V) to enable the pressure of the reaction kettle to be 4bar, starting an LED ultraviolet lamp (with the wavelength of 254nm) with the power of 200W, irradiating the reaction kettle for 120s by using ultraviolet light at room temperature, and transferring the reaction kettle to an active fluorine gas mixed gas storage tank for standby after activation is finished.
Example 2
Adding 26.6g (62.5mmol) of N, N-bis (pentafluoropropionyloxypropyl) amine and 1.1g (18mmol) of potassium fluoride into a 1.8L photocatalytic reaction kettle equipped with a mechanical stirring and a condenser, adding 400mL of anhydrous acetonitrile, replacing with high-purity nitrogen twice, starting stirring, introducing active nitrogen trifluoride at 30 ℃ for 10h at 60mL/min, reacting at 1bar, heating to 120 ℃, stirring vigorously for 5h, reducing the temperature of the reaction system to-60 ℃, introducing a mixed gas of oxygen and carbon dioxide (the flow ratio of oxygen to carbon dioxide is 7:3), starting a high-pressure ultraviolet lamp with the power of 500W, introducing hexafluorobutadiene and 2,3,3, 3-tetrafluoropropene according to a certain ratio, controlling the molar ratio of oxygen, hexafluorobutadiene and 2,3,3, 3-tetrafluoropropene to be 3.0: 0.1, keeping the reaction pressure at 2bar, keeping the ultraviolet lamp irradiating for 30h, closing the ultraviolet lamp, stopping introducing the fluoroolefin monomer, continuing introducing the oxygen and carbon dioxide mixed gas for 30min, stopping, gradually increasing the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of the monomer fluoroolefin is about 17mol, preparing the double-acyl end group polymer, finally opening the ultraviolet lamp, carrying out fluorination treatment by adopting active fluorine gas mixed gas at 120 ℃ for 10h to obtain double-end perfluoropolyether, and carrying out fluorination treatment by using the double-end perfluoropolyether19F-NMR nuclear magnetic resonance spectroscopy analysis shows that the average molecular weight is about 23000Da, weighing is carried out, and the calculated yield is about 84% based on the input of the fluoroolefin monomer.
The preparation method of the active nitrogen trifluoride comprises the following steps: vacuumizing a 1L stainless steel photocatalytic reaction kettle with a light source cold trap, replacing with nitrogen for three times, introducing nitrogen trifluoride, heating the reaction kettle to 40 ℃ to ensure that the pressure of the reaction kettle is 3.5bar, introducing cooling circulating water into the light source cold trap, then starting a high-pressure ultraviolet mercury lamp (a full-spectrum light-emitting light source with an effective wavelength range of 200 and 420nm) with the power of 500W, irradiating by ultraviolet light for 30s, and after activation, transferring the activated nitrogen trifluoride into an active nitrogen trifluoride storage tank for later use.
Example 3
Adding 44.2g (0.125mol) of N, N-bis (trifluoroacetoxybutyl) amine and 0.9g (8.5mmol) of rubidium fluoride into a 1.25L photocatalytic reaction kettle provided with a mechanical stirrer and a condenser, replacing the high-purity nitrogen for two times, reducing the reaction temperature to-20 ℃, introducing 200mL of heptafluoropropane, starting stirring, introducing active carbonyl fluoride mixed gas for 15 hours at the rate of 40mL/min, reacting at the pressure of 4bar, heating to 100 ℃, violently stirring for 6 hours, controlling the temperature of the condenser to be 30 ℃, reducing the temperature of a reaction system to-50 ℃, then adding about 850mL of pentafluoroethane, introducing oxygen and carbon dioxide mixed gas (the flow ratio of the oxygen to the carbon dioxide is 6:4), starting an LED ultraviolet lamp (the wavelength is 308nm) with the power of 100W, introducing tetrafluoroethylene, hexafluoropropylene and trifluoroethylene according to a certain proportion, and controlling the oxygen, the fluorine content of the fluorine-containing ethylene and the fluorine, The mol ratio of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride is 2.0:0.5:0.1:0.4, the reaction pressure is 4bar, after the ultraviolet lamp is kept irradiating for 25 hours, the ultraviolet lamp is closed, the fluoroolefin monomer is stopped being introduced, the oxygen and carbon dioxide mixed gas is continuously introduced for 30 minutes and then is stopped, the reaction temperature is gradually increased to the room temperature, unreacted perfluoroolefin and fluoroolefin monomer are condensed and recovered, the effective input amount of the monomer fluoroolefin is about 16mol, the bisacyl end group polymer is prepared, finally, the ultraviolet lamp is started, the active fluorine gas mixed gas is adopted for fluorination treatment, the temperature is 50 ℃, the time is 24 hours, the double-end perfluoropolyether is obtained, and the double-end perfluoropolyether is obtained by the steps of19F-NMR nuclear magnetic resonance spectroscopy analysis shows that the average molecular weight is 11500Da, weighing is carried out, and the calculated yield is about 68% based on the input amount of the fluoroolefin monomer.
The preparation method of the active carbonyl fluoride mixed gas used in the embodiment comprises the following steps: vacuumizing a 1L stainless steel photocatalytic reaction kettle with a light source cold trap, replacing with argon for three times, introducing 60% carbonyl fluoride/argon mixed gas (V/V) to ensure that the pressure of the reaction kettle is 1bar, starting an LED ultraviolet lamp (with the wavelength of 308nm) with the power of 100W, irradiating the reaction kettle with ultraviolet light for 180s at the temperature of 25 ℃, and transferring the reaction kettle to an active carbonyl fluoride mixed gas storage tank for later use after activation is finished.
Example 4
Adding 51.4g (0.125mol) of bis (pentafluoropropionyloxyethyl) methylamine, 1.5g (10.0mmol) of cesium fluoride and 400mL of 1,2, 2-trifluoro-1, 1, 2-trichloroethane into a 1.25L photocatalytic reaction kettle equipped with a mechanical stirring and a condenser, replacing the high-purity nitrogen gas for two times, starting stirring, introducing an active fluorine gas mixed gas at room temperature of 50mL/min for reaction for 12 hours under the reaction pressure of 2bar, then heating to 90 ℃ and stirring vigorously for 9 hours, then reducing the temperature of the reaction system to-40 ℃, then introducing oxygen, starting a high-pressure ultraviolet mercury lamp with the power of 1000W, then introducing hexafluorobutadiene and 1-chloro-2, 3,3, 3-tetrafluoropropene according to a certain proportion, controlling the molar ratio of the oxygen, the hexafluorobutadiene, the 1-chloro-2, 3,3, 3-tetrafluoropropene to be 2.0: 0.6, keeping the reaction pressure at 0.5bar, keeping the ultraviolet lamp irradiating for 20h, closing the ultraviolet lamp, stopping introducing fluoroolefin monomer, continuing introducing oxygen for 30min, stopping introducing oxygen, gradually raising the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of the fluoroolefin monomer is about 12.5mol, preparing the bisacyl end group polymer, finally opening the ultraviolet lamp, carrying out fluorination treatment by adopting active fluorine gas mixture, keeping the temperature at 100 ℃, keeping the time at 15h, obtaining double-end perfluoropolyether, and carrying out fluorination treatment by using a double-end perfluoropolyether19F-NMR spectroscopy analysis showed that the average molecular weight was about 8700Da, and the weight was calculated as a fluoroolefin monomer feed in about 80% yield.
The preparation method of the active fluorine gas mixture comprises the following steps: vacuumizing a 1L stainless steel photocatalytic reaction kettle with a light source cold trap, replacing nitrogen for three times, introducing 30% fluorine gas/nitrogen mixed gas (V/V) to ensure that the pressure of the reaction kettle is 4bar, starting a high-pressure ultraviolet mercury lamp (a full-spectrum light source, the effective wavelength range of 200-420nm) with the power of 1000W, irradiating the reaction kettle for 30s by using ultraviolet light at room temperature, and transferring the reaction kettle to an active fluorine gas mixed gas storage tank for standby after activation.
Example 5
Adding 21.2g (62.5mmol) of bis (trifluoroacetoxyethyl) propylamine, 0.7g (5.0mmol) of silver fluoride and HFE-347400 mL of hydrofluoroether into a 1.25L photocatalytic reaction kettle equipped with a mechanical stirrer and a condenser, replacing with high-purity nitrogen twice, starting stirring, introducing an active fluorine gas mixed gas prepared according to the method in example 1 at-20 ℃ for reaction for 12 hours at a reaction pressure of 2bar, then heating to 80 ℃, violently stirring for 9 hours, then reducing the temperature of a reaction system to-70 ℃, then introducing 900mL of difluorochloromethane, then introducing an oxygen-carbon dioxide mixed gas (the flow ratio of the oxygen to the carbon dioxide is 7:3), starting an LED ultraviolet lamp (wavelength is 365nm) with the power of 300W, further introducing tetrafluoroethylene, 1-chloro-3, 3, 3-trifluoropropene according to a certain proportion, during the period, the molar ratio of oxygen to tetrafluoroethylene to 1-chloro-3, 3, 3-trifluoropropene is controlled to be 2.5:0.8:0.2, the reaction pressure is 1bar, the ultraviolet lamp is kept to irradiate for 20 hours, then the ultraviolet lamp is closed, the fluoroolefin monomer is stopped being introduced, the oxygen and carbon dioxide mixed gas is continuously introduced for 30 minutes and then stopped, the reaction temperature is gradually increased to the room temperature, the unreacted perfluoroolefin and fluoroolefin monomer are condensed and recovered, the effective input amount of the fluoroolefin monomer is about 12.5mol, the diacyl-terminated polymer is prepared, finally, the ultraviolet lamp is opened, the active fluorine gas mixed gas prepared according to the method of the embodiment 1 is adopted for fluorination treatment, the temperature is 90 ℃, the time is 20 hours, the double-ended perfluoropolyether is obtained, and the double-ended perfluoropolyether is prepared by the method of the embodiment 119F-NMR nuclear magnetic resonance spectroscopy analysis shows that the average molecular weight is about 15600Da, weighing is carried out, and the calculated yield is about 72 percent based on the input quantity of the fluoroolefin monomer.
Example 6
Adding 47.7g (0.125mol) of bis (trifluoroacetoxybutyl) ethylamine, 2.4g (15.7mmol) of cesium fluoride and 200mL of Galden series HT50 solvent from Solvay company into a 0.6L photocatalytic reaction kettle with a mechanical stirrer and a condenser, replacing high-purity nitrogen for two times, starting stirring, introducing the active fluorine gas mixed gas prepared according to the method in example 1 at the temperature of-10 ℃ for reaction for 15 hours at the reaction pressure of 2bar, heating to 100 ℃, violently stirring for 10 hours, reducing the temperature of the reaction system to-60 ℃, introducing oxygen, starting an LED ultraviolet lamp (wavelength of 254nm) with the power of 50W, and then, according to a certain ratioIn the process, hexafluoropropylene and 1,1,1,4,4, 4-hexafluoro-2-butene are introduced, the molar ratio of oxygen to hexafluoropropylene and 1,1,1,4,4, 4-hexafluoro-2-butene is controlled to be 2.5:0.5:0.5, the reaction pressure is 1bar, after the ultraviolet lamp irradiation is maintained for 10 hours, the ultraviolet lamp is turned off, the introduction of fluoroolefin monomers is stopped, the introduction of oxygen is continued for 30 minutes, the reaction temperature is gradually increased to the room temperature, unreacted perfluoroolefin and fluoroolefin monomers are condensed and recovered, the effective input amount of fluoroolefin monomers is about 6.25mol, a bisacyl end group-terminated polymer is prepared, finally, the ultraviolet lamp is turned on again, the fluorination treatment is carried out by adopting the active fluorine gas mixed gas prepared according to the method of the embodiment 1, the temperature is 90 ℃, the time is 20 hours, double-end perfluoropolyether is obtained, and the double-end perfluoropolyether is obtained by the following steps of19F-NMR spectroscopy analysis showed that the average molecular weight was about 5700Da, and the weight was calculated as a yield of about 78% based on the fluoroolefin monomer feed.
Example 7
Adding 27.5g (62.5mmol) of bis (pentafluoropropionyloxypropyl) methylamine, 1.4g (9.0mmol) of cesium fluoride and 400mL of 1,2, 2-trifluoro-1, 1, 2-trichloroethane into a 1.8L photocatalytic reaction kettle provided with a mechanical stirring and condenser, replacing the high-purity nitrogen for two times, starting stirring, introducing the active fluorine gas mixed gas prepared according to the method in example 1 at 50mL/min at room temperature for reaction for 15 hours, stopping introducing the active fluorine gas mixed gas, heating to 90 ℃, violently stirring for 7 hours, reducing the temperature of the reaction system to-60 ℃, introducing 1.6L of difluorodichloromethane, introducing oxygen and carbon dioxide mixed gas (the flow ratio of the oxygen to the carbon dioxide is 7:3), starting an LED ultraviolet lamp (the wavelength is 254nm) with the power of 100W, introducing tetrafluoroethylene according to a certain ratio, introducing a nitrogen gas into the reaction kettle, introducing a nitrogen gas mixture into the reaction kettle, and introducing a nitrogen gas mixture of the hydrogen gas and the hydrogen gas into the reaction kettle at a certain ratio, Vinylidene fluoride, controlling the reflux temperature of a condenser to be 77 ℃ below zero, controlling the molar ratio of oxygen to tetrafluoroethylene to vinylidene fluoride to be 2.0:0.9:0.1, controlling the reaction pressure to be 2bar, keeping the ultraviolet lamp irradiating for 20h, closing the ultraviolet lamp, stopping introducing the fluoroolefin monomer, continuing to introduce the oxygen and carbon dioxide mixed gas for 30min, stopping introducing the oxygen and carbon dioxide mixed gas, gradually raising the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of the monomer fluoroolefin is about 21.9mol, preparing the diacyl-terminated polymer, finally starting the ultraviolet lamp,carrying out fluorination treatment by adopting active fluorine gas mixture at the temperature of 100 ℃ for 15 hours to obtain double-end perfluoropolyether19F-NMR spectroscopy analysis showed an average molecular weight of about 25200Da and the yield was about 70% by weight, calculated as the fluoroolefin monomer feed.
Example 8
The double-end perfluoropolyether prepared in the embodiments 1 to 7 is subjected to equal mass sample taking, merging, molecular distillation is adopted for fraction segmentation, double-end perfluoropolyethers with different average molecular weights are obtained, the corresponding average molecular weights, viscosities and pour points are tested, and viscosity indexes are calculated, and the results are shown in table 1.
TABLE 1 average molecular weight, viscosity, pour Point of the two-terminal perfluoropolyethers
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (9)
1. A double-end perfluoropolyether is characterized in that the structural formula of the double-end perfluoropolyether is shown as a formula (I):
wherein, the first and second connecting parts are connected with each other; x is F, CF3-，C2F5Or C3F7(ii) a A is CF3-or C2F5-; b is CF3-or C2F5-; a1, a2, b1, b2, c1 and c2 are all greater than or equal to 1; n is 0, 1 or 2; the average molecular weight of the double-end perfluoropolyether is 4000-30000 Da.
2. A process for the preparation of the double-ended perfluoropolyether of claim 1, comprising:
(1) in the presence of metal fluoride, N, N-bis (perfluoroalkyl acyloxy alkyl) amine or bis (perfluoroalkyl acyloxy alkyl) alkylamine is fluorinated by an active fluorine source to obtain a dialkanolamine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by irradiating a fluorinating reagent with ultraviolet light, wherein the fluorinating reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas;
(2) under the irradiation of ultraviolet light, carrying out photooxidation polymerization on a perfluoroolefin monomer, a second fluorine-containing olefin monomer, a binary alcohol amine fluoride and oxygen or oxygen carbon dioxide mixed gas to obtain a diacyl-terminated polymer; the photo-oxidative polymerization reaction conditions are as follows: the reaction temperature is-70 ℃ to-25 ℃, and the reaction pressure is 0.5bar to 4 bar; the second fluorine-containing olefin monomer is a C2-C4 fluorine-containing olefin;
(3) and (3) carrying out fluorination treatment on the diacyl-terminated polymer at the temperature of between 50 and 120 ℃ by adopting an active fluorine source to obtain the double-ended perfluoropolyether.
3. The process according to claim 2, wherein the N, N-bis (perfluoroalkanoyloxyalkyl) amine is selected from the group consisting of N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (pentafluoropropionyloxybutyl) amine, N-bis (trifluoroacetyloxyethyl) amine, N-bis (trifluoroacetyloxypropyl) amine and N, N-bis (trifluoroacetyloxybutyl) amine; the bis (perfluoroalkanoyloxyalkyl) alkylamine is selected from bis (pentafluoropropionyloxyethyl) methylamine, bis (pentafluoropropionyloxyethyl) ethylamine, bis (pentafluoropropionyloxyethyl) propylamine, bis (trifluoroacetyloxyethyl) methylamine, bis (trifluoroacetyloxyethyl) ethylamine, bis (trifluoroacetyloxyethyl) propylamine, bis (pentafluoropropionyloxypropyl) methylamine, bis (pentafluoropropionyloxypropyl) ethylamine, bis (trifluoroacetyloxypropyl) methylamine, bis (trifluoroacetyloxypropyl) ethylamine, bis (pentafluoropropionyloxybutyl) methylamine, bis (pentafluoropropionyloxybutyl) ethylamine, bis (trifluoroacetyloxybutyl) methylamine or bis (trifluoroacetyloxybutyl) ethylamine.
4. The method according to claim 2, wherein the perfluoroolefin monomer is one or more selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and hexafluorobutadiene.
5. The method according to claim 2, the second fluorine-containing olefin monomer is one or more selected from vinylidene fluoride, trifluoroethylene, 3,3, 3-trifluoropropene, 2,3,3, 3-tetrafluoropropene, 1,1,1, 3-tetrafluoropropene, 1,1,2, 3-pentafluoropropene, 1,1,1,3, 3-pentafluoropropene, 1,1,1,4,4, 4-hexafluoro-2-butene, 1-chloro-3, 3, 3-trifluoropropene, 2-chloro-3, 3, 3-trifluoropropene, 1, 2-dichloro-3, 3, 3-trifluoropropene, 1-chloro-2, 3,3, 3-tetrafluoropropene or 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene.
6. The preparation method according to claim 2, wherein the volume ratio of oxygen to carbon dioxide in the oxygen-carbon dioxide mixed gas is 7-10: 0-3.
7. The process according to claim 2, wherein the photooxidative polymerization reaction is carried out at a temperature of-60 ℃ to-40 ℃.
8. The method of claim 2, wherein the molar amount of the dialkanolamine fluoride to the total molar amount of the monomers is in a ratio of 1: 50 to 350.
9. The method of claim 2, further comprising fractionating the resulting double-ended perfluoropolyether by molecular distillation to obtain double-ended perfluoropolyethers of different average molecular weights.
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