CN114395117B - 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 perfluorinated polyether and a preparation method thereof. The structural formula of the double-end perfluoropolyether is shown as the formula (I); the disclosed preparation method comprises the steps of under the existence of metal fluoride, carrying out active fluorine source fluorination on N, N-bis (perfluoroalkyl acyloxyalkyl) amine or bis (perfluoroalkyl acyloxyalkyl) alkylamine to obtain glycol amine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by ultraviolet irradiation of a fluoridation reagent, wherein the fluoridation reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas; then under the irradiation of ultraviolet light, the perfluorinated olefin monomer, the second fluorinated olefin monomer, the glycol amine fluoride and oxygen are subjected to photo-oxidation polymerization to obtain a diacyl end group polymer; and then carrying out fluorination treatment on the diacyl end group polymer by adopting an active fluorine source at 50-120 ℃ to obtain double-end perfluoropolyether. The invention is used for preparing double-end perfluor polyether containing nitrogen atoms in the main chain structure.
Description
Technical Field
The invention belongs to the technical field of perfluoropolyethers, and particularly relates to double-ended perfluoropolyether prepared by photo-oxidative polymerization of mixed gas of perfluoroolefin, fluoroolefin, glycol amine fluoride and oxygen carbon dioxide and a preparation method thereof.
Background
The perfluoropolyether is a polymer compound produced by substituting hydrogen in alkane with fluorine, oxygen or the like, and contains only C, F, O elements in the molecule. Because of strong electronegativity and pseudo-effect of fluorine atoms and shielding effect of C-F bond on main chain C-C bond, perfluoropolyether 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, electrics, chemical machinery, aerospace, nuclear industry and the like.
At present, two main methods for preparing perfluoropolyethers exist. The first is anion polymerization represented by hexafluoropropylene oxide, and the prepared perfluoropolyether has small molecular weight, generally between 1000 and 7000, low viscosity index (less than 150) and difficult to meet the lubrication sealing use requirement under severe conditions such as wide temperature range, although the method has simple process, safe and controllable process and higher reaction yield. The second method is to prepare perfluoropolyether by oxidizing and polymerizing perfluoroolefin, which is usually prepared by using a kettle reactor or a photochemical reactor, taking perfluoroolefin and oxygen as raw materials, initiating polymerization by chemical initiator or ultraviolet light, and then performing fluorination treatment to obtain stable perfluoropolyether. The process for preparing perfluoropolyethers by chemical initiators is generally extremely difficult to control, and the resulting perfluoropolyether products have low molecular weights and it is difficult to obtain products with high degrees of polymerization, as disclosed in U.S. Pat. No. 3,182 as F 2 As an initiator, the molecular weight of the perfluoropolyether peroxide obtained by reacting tetrafluoroethylene with oxygen in a solvent is only about 3000 at maximum. CN1167124A reports on COF in the presence of a chemical initiator containing at least one F-X bond 2 The oxidation polymerization of tetrafluoroethylene is carried out in a solvent having a molar content of more than 8% under a reaction pressure of 0 to 15bar to obtain a perfluoropolyether having a PO value (PO value is the mass of active oxygen contained in 100g of the compound) of less than 4 and having a number average molecular weight of 10000 or less although the number average molecular weight is improved. US10029981 discloses a process for preparing perfluoropolyether acyl fluorides by reacting perfluoroolefins with oxygen in a microreactor under irradiation of ultraviolet light, the overall yields being below 40%, although the reaction gives products having average molecular weights of 5000 to 20000. U.S. Pat. Nos. 4451646, 3715378, 3847978 disclose methods for preparing perfluoropolyethers by photocatalytic oxidative polymerization, which methods are generally free radical reaction mechanisms involving oxygen and a centerThe technology is complex, the technical difficulty is high, and continuous improvement and optimization are also required to realize the efficient and safe preparation of high-molecular-weight perfluoropolyether. In addition, with the continuous development and expansion of the application of the perfluoropolyether compound, new requirements are also put forward on the molecular weight and structure of the perfluoropolyether, and the realization of the modification and regulation of the main chain structure of the perfluoropolyether while preparing the perfluoropolyether becomes particularly important.
Disclosure of Invention
In response to the shortcomings or drawbacks of the prior art, the present invention provides a double ended perfluoropolyether.
The structural formula of the double-end perfluorinated polyether provided by the invention is shown as the formula (I):
wherein; x is F, CF 3- ，C 2 F 5 Or C 3 F 7 The method comprises the steps of carrying out a first treatment on the surface of the A is CF 3 -or C 2 F 5 -; b is CF 3 -or C 2 F 5 -; a1, a2, b1, b2, c1, c2 are all 1 or more; n=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 acyloxyalkyl) amine or bis (perfluoroalkyl acyloxyalkyl) alkylamine is fluorinated by an active fluorine source to obtain glycol amine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by ultraviolet irradiation of a fluorination reagent, wherein the fluorination reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas;
(2) Under the irradiation of ultraviolet light, the perfluorinated olefin monomer, the second fluorinated olefin monomer, the glycol amine fluoride and oxygen or oxygen carbon dioxide mixed gas are subjected to photo-oxidative polymerization to obtain a diacyl end group polymer; the photo-oxidative polymerization reaction conditions are as follows: the reaction temperature is between 70 ℃ below zero and 25 ℃ below zero, and the reaction pressure is between 0.5 and 4bar; the second fluoroolefin monomer is a C2-C4 fluoroolefin;
(3) And (3) carrying out fluorination treatment on the diacyl end group polymer by adopting an active fluorine source at 50-120 ℃ to obtain double-end perfluoropolyether.
Alternatively, the N, N-bis (perfluoroalkylacyloxyalkyl) amine is selected from the group consisting of N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (pentafluoropropionyloxybutyl) amine, N-bis (trifluoroacetoxyethyl) amine, N-bis (trifluoroacetoxypropyl) amine, and N, N-bis (trifluoroacetoxybutyl) amine; the bis (perfluoroalkylacyloxyalkyl) alkylamine is selected from the group consisting of bis (pentafluoropropionyloxyethyl) methylamine, bis (pentafluoropropionyloxyethyl) ethylamine, bis (pentafluoropropionyloxyethyl) propylamine, bis (trifluoroacetoxyethyl) methylamine, bis (trifluoroacetoxyethyl) ethylamine, bis (trifluoroacetoxyethyl) propylamine, bis (pentafluoropropionyloxypropyl) methylamine, bis (pentafluoropropionyloxypropyl) ethylamine, bis (trifluoroacetoxypropyl) methylamine, bis (trifluoroacetoxypropyl) ethylamine, bis (pentafluoropropionyloxybutyl) methylamine, bis (pentafluoropropionyloxybutyl) ethylamine, bis (trifluoroacetoxybutyl) methylamine, and bis (trifluoroacetoxybutyl) ethylamine.
Optionally, the perfluoroolefin monomer is selected from one or more than two of tetrafluoroethylene, hexafluoropropylene and hexafluorobutadiene.
Alternatively to this, the method may comprise, the second fluoroolefin monomer is selected from vinylidene fluoride, trifluoroethylene, 3-trifluoropropene, 2, 3-tetrafluoropropene 1, 3-tetrafluoropropene, 1,2, 3-pentafluoropropene, 1, 3-pentafluoropropene, 1, 4-hexafluoro-2-butene 1, 3-tetrafluoropropene, 1,2, 3-pentafluoropropene 1, 3-pentafluoropropene, 1, 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 ratio of glycol amine fluoride to total molar amount of monomer is 1: 50-350.
The method further comprises the step of carrying out fraction segmentation on the obtained double-end perfluoropolyether by molecular distillation to obtain double-end perfluoropolyethers with different average molecular weights.
The invention realizes modification and regulation of the main chain structure of the perfluoropolyether, synthesizes the novel double-end perfluoropolyether with nitrogen atoms in the main chain, and provides a new thought for modification of the perfluoropolyether. 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 specifically stated otherwise, the terms herein are understood or implemented using existing related methods according to the knowledge of one of ordinary skill in the relevant art.
Based on the disclosure of the scheme of the invention, the person skilled in the art can perform optimization selection on the related parameters such as the material dosage relation, the reaction temperature, the reaction time, the atmosphere composition, the ventilation amount and the like in the scheme of the invention, and the scheme after optimization selection is not limited to the specific range and the examples disclosed by the invention. The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The average molecular weight of the double ended perfluoropolyethers in the following examples was determined using a Bruker 500MHz NMR spectrometer 19 F-NMR test analysis; the viscosity of the double-ended perfluoropolyether was measured using an australian An Dongpa company MCR302 viscometer, test conditions: heating rate is 5 ℃/min, test temperature range is 20-120 ℃, and viscosity index of the sample is calculated by adopting national standard GB/T1995-1998; the pour point of the perfluoropolyether is determined using national standard GB/T3535-2006.
Example 1
In a condenser equipped with mechanical stirring25.0g (62.5 mmol) of N, N-bis (pentafluoropropionoxyethyl) amine and 1.5g (10.0 mmol) of cesium fluoride are added into a 1.25L photocatalytic reaction kettle, 400mL of 1, 2-trifluoro-1, 2-trichloroethane is replaced by high-purity nitrogen twice, stirring is started, an active fluorine gas mixture is introduced at room temperature for reaction for 12h at 50mL/min, the reaction pressure is 2bar, the temperature is raised to 80 ℃ for vigorous stirring for 9h, the temperature of a condenser is controlled to be about 30 ℃, the temperature of a reaction system is reduced to minus 30 ℃, then 550mL of 1, 2-trifluoro-1, 2-trichloroethane is added, an oxygen and carbon dioxide mixture (the flow ratio of oxygen to carbon dioxide is 8:2) is introduced, an LED ultraviolet lamp (wavelength 254 nm) with power of 200W is started, introducing tetrafluoroethylene and 2-chloro-3, 3-trifluoropropene according to a certain proportion, controlling the mol ratio of oxygen to tetrafluoroethylene to 2-chloro-3, 3-trifluoropropene to be 2.5:0.7:0.3 during the period, keeping the reaction pressure of 1bar, keeping the irradiation of an ultraviolet lamp for 20 hours, closing the ultraviolet lamp, stopping introducing fluoroolefin monomer, continuing to introduce oxygen and carbon dioxide mixed gas for 30 minutes, stopping, gradually raising the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of fluoroolefin monomer is about 15mol, preparing a diacyl end group polymer, finally, starting the ultraviolet lamp, carrying out fluorination treatment by adopting active fluorine gas mixed gas, and obtaining double-end perfluorinated polyether by the temperature of 100 ℃ for 15 hours 19 F-NMR spectrum test analysis shows that the average molecular weight is about 18000Da, and the yield is about 75% based on the fluoroolefin monomer.
The preparation method of the active fluorine gas mixture comprises the following steps: after a 1L stainless steel photocatalysis reaction kettle with a light source cold trap is vacuumized and replaced by nitrogen for three times, 30 percent fluorine/nitrogen mixed gas (V/V) is introduced, so that the pressure of the reaction kettle is 4bar, an LED ultraviolet lamp (wavelength 254 nm) with the power of 200W is started, ultraviolet light is irradiated for 120s at room temperature, and after activation is completed, the reaction kettle is transferred to an active fluorine gas mixed gas storage tank for standby.
Example 2
Into a 1.8L photocatalytic reactor equipped with a mechanical stirrer and a condenser, 26.6g (62.5 mmol) of N, N-bis (pentafluoropropiooxypropyl) amine and 1.1g (18 mmol) of potassium fluoride were added, and 400mL of anhydrous acetonitrile was added thereto, followed by replacement with high-purity nitrogen gasAfter two times, stirring is started, active nitrogen trifluoride is introduced at 30 ℃ for reaction for 10 hours at 60ml/min, the reaction pressure is 1bar, then the temperature is raised to 120 ℃ for intense stirring for 5 hours, then the temperature of a reaction system is reduced to minus 60 ℃, then oxygen and carbon dioxide mixed gas (the flow ratio of oxygen to carbon dioxide is 7:3) is introduced, a high-pressure ultraviolet lamp with the power of 500W is started, hexafluorobutadiene and 2, 3-tetrafluoropropene are introduced according to a certain proportion, during the period, the molar ratio of oxygen, hexafluorobutadiene and 2, 3-tetrafluoropropene is controlled to be 3.0:0.9:0.1, the reaction pressure is 2bar, after the ultraviolet lamp is kept to irradiate for 30 hours, the ultraviolet lamp is turned off, the introduction of fluoroolefin monomers is stopped, the continuous introduction of oxygen and carbon dioxide mixed gas is stopped after 30 minutes, the reaction temperature is gradually raised to room temperature, the unreacted perfluoroolefin and fluoroolefin monomers are condensed and recovered, the effective input amount of monomer fluoroolefin is about 17mol, the diacyl polymer is prepared, and finally the ultraviolet lamp is turned on, the ultraviolet lamp is subjected to the treatment at the temperature of the total fluorine for 10 hours, the total fluorinated gas is carried out for the reaction time of 120 hours, and the polyether is obtained after the ultraviolet lamp is subjected to the total fluorine treatment, and the total fluorine is continuously heated to the fluoroolefin, and the total fluorine is continuously heated to the total fluorine gas 19 F-NMR spectrum analysis shows that the average molecular weight is about 23000Da, and the yield is about 84% based on the fluoroolefin monomer.
The preparation method of the active nitrogen trifluoride comprises the following steps: vacuumizing a 1L stainless steel photocatalysis reaction kettle with a light source cold trap, replacing nitrogen for three times, introducing nitrogen trifluoride, heating the reaction kettle to 40 ℃, enabling the pressure of the reaction kettle to be 3.5bar, introducing cooling circulating water into the light source cold trap, then starting a high-pressure ultraviolet mercury lamp (a full spectrum luminous light source with the effective wavelength range of 200-420 nm) with the power of 500W, irradiating ultraviolet light for 30s, and transferring the activated product to an active nitrogen trifluoride storage tank for standby.
Example 3
Adding 44.2g (0.125 mol) of N, N-bis (trifluoroacetoxybutyl) amine and 0.9g (8.5 mmol) of rubidium fluoride into a 1.25L photocatalysis reaction kettle with a mechanical stirring and a condenser, replacing high-purity nitrogen twice, reducing the reaction temperature to minus 20 ℃, introducing 200mL of heptafluoropropane, starting stirring, introducing 15h of active carbonyl fluoride mixed gas at 40mL/min, reacting at 4bar, then heating to 100 ℃, vigorously stirring for 6h, controlling the temperature of the condenser at 30 ℃, and then reducingThe temperature of the reaction system is up to minus 50 ℃, then, pentafluoroethane is added into the reaction system for about 850mL, a mixed gas of oxygen and carbon dioxide (the flow ratio of the oxygen to the carbon dioxide is 6:4), an LED ultraviolet lamp (the wavelength is 308 nm) with the power of 100W is started, tetrafluoroethylene, hexafluoropropylene and trifluoroethylene are then added according to a certain proportion, during the period, the mol ratio of the oxygen, the tetrafluoroethylene, the hexafluoropropylene and the vinylidene fluoride is controlled to be 2.0:0.5:0.1:0.4, the reaction pressure is 4bar, the ultraviolet lamp is kept to irradiate for 25 hours, then, the ultraviolet lamp is turned off, the introduction of fluoroolefin monomers is stopped, the continuous introduction of the mixed gas of the oxygen and the carbon dioxide is stopped after 30 minutes, the reaction temperature is gradually increased to room temperature, the unreacted perfluoroolefin and fluoroolefin monomers are recovered by condensation, the effective input amount of the fluoroolefin monomers is about 16mol, the diacyl end group polymer is prepared, and finally, the ultraviolet lamp is turned on, the active fluoroolefin mixture is adopted for fluorination treatment at 50 ℃ for 24 hours, and the double-end perfluoropolyether is obtained 19 F-NMR spectrum analysis shows that the average molecular weight is about 11500Da, and the yield is about 68% based on the fluoroolefin monomer.
The preparation method of the active carbonyl fluoride mixed gas used in the embodiment comprises the following steps: after a 1L stainless steel photocatalysis reaction kettle with a light source cold trap is vacuumized and replaced by argon for three times, 60 percent of carbonyl fluoride/argon mixed gas (V/V) is introduced, so that the pressure of the reaction kettle is 1bar, an LED ultraviolet lamp (with the wavelength of 308 nm) with the power of 100W is started, ultraviolet light is irradiated for 180 seconds at the temperature of 25 ℃, and after activation is completed, the reaction kettle is transferred to an active carbonyl fluoride mixed gas storage tank for standby.
Example 4
51.4g (0.125 mol) of bis (pentafluoropropionyloxyethyl) methylamine and 1.5g (10.0 mmol) of cesium fluoride are added into a 1.25L photocatalytic reaction kettle equipped with a mechanical stirring and a condenser, 400mL of 1, 2-trifluoro-1, 2-trichloroethane is replaced by high-purity nitrogen twice, stirring is started, 50mL/min of active fluorine gas mixture is introduced at room temperature for reaction for 12h, the reaction pressure is 2bar, the temperature is raised to 90 ℃ for vigorous stirring for 9h, the temperature of the reaction system is reduced to minus 40 ℃, oxygen is introduced, a high-pressure ultraviolet mercury lamp with the power of 1000W is started, and hexafluorobutadiene and 1-chloro-2, 3-tetrafluoropropene are introduced according to a certain proportion during the reactionControlling the mol ratio of oxygen, hexafluorobutadiene and 1-chloro-2, 3-tetrafluoropropene to be 2.0:0.4:0.6, keeping the reaction pressure to be 0.5bar, keeping the ultraviolet lamp to irradiate for 20 hours, turning off the ultraviolet lamp, stopping introducing fluoroolefin monomer, continuing to introduce oxygen for 30 minutes, stopping, gradually raising the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of monomer fluoroolefin is about 12.5mol, preparing a diacyl end group polymer, finally turning on the ultraviolet lamp, carrying out fluorination treatment by adopting active fluorine gas mixture gas at the temperature of 100 ℃ for 15 hours, and obtaining double-end perfluoropolyether, wherein the reaction temperature is gradually raised to room temperature, and the total fluorine-containing polyether is obtained by the steps of 19 F-NMR spectrum analysis shows that the average molecular weight is about 8700Da, and the yield is about 80% based on the fluoroolefin monomer.
The preparation method of the active fluorine gas mixture comprises the following steps: after a 1L stainless steel photocatalysis reaction kettle with a light source cold trap is vacuumized and replaced by nitrogen for three times, 30 percent fluorine/nitrogen mixed gas (V/V) is introduced, so that the pressure of the reaction kettle is 4bar, a high-pressure ultraviolet mercury lamp (a full spectrum light-emitting light source with the effective wavelength range of 200-420 nm) with the power of 1000W is started, ultraviolet light is irradiated for 30 seconds at room temperature, and after activation is completed, the reaction kettle is transferred to an active fluorine gas mixed gas storage tank for standby.
Example 5
21.2g (62.5 mmol) of bis (trifluoroacetoxyethyl) propylamine and 0.7g (5.0 mmol) of silver fluoride are added into a 1.25L photocatalysis reaction kettle with a mechanical stirring and a condenser, after twice replacement of high-purity nitrogen, stirring is started, the active fluorine gas mixture prepared according to the method in example 1 is introduced at 50mL/min at-20 ℃ for reaction for 12 hours, the reaction pressure is 2bar, then the temperature is raised to 80 ℃ for vigorous stirring for 9 hours, the temperature of the reaction system is reduced to-70 ℃, then 900mL of difluoromethane is introduced, then the mixed gas of oxygen and carbon dioxide (the flow ratio of oxygen to carbon dioxide is 7:3), an LED ultraviolet lamp (with the wavelength of 365 nm) with the power of 300W is started, tetrafluoroethylene, 1-chloro-3, 3-trifluoropropene are introduced according to a certain proportion, during the period, the molar ratio of oxygen, tetrafluoroethylene, 1-chloro-3, 3-trifluoropropene is controlled to be 2.5:0.8:0.2, the pressure is controlled, the ultraviolet lamp is stopped for reaction for 20 hours, and after the ultraviolet lamp is stopped for reaction for 20 hoursStopping introducing fluoroolefin monomer, continuing introducing oxygen and carbon dioxide mixed gas for 30min, stopping, gradually raising the reaction temperature to room temperature, condensing and recovering unreacted perfluoroolefin and fluoroolefin monomer, wherein the effective input amount of monomer fluoroolefin is about 12.5mol, preparing a diacyl end group polymer, finally starting an ultraviolet lamp, performing fluorination treatment by adopting the active fluorine gas mixed gas prepared according to the method of the embodiment 1, obtaining double-end perfluoropolyether, and performing fluorination treatment at 90 ℃ for 20h 19 F-NMR spectrum analysis shows that the average molecular weight is about 15600Da, and the yield is about 72% based on the fluoroolefin monomer.
Example 6
47.7g (0.125 mol) of bis (trifluoroacetoxybutyl) ethylamine and 2.4g (15.7 mmol) of cesium fluoride are added into a 0.6L photocatalysis reaction kettle provided with a mechanical stirring and a condenser, 200mL of Galden series HT50 solvent of Solvay company are replaced twice by high-purity nitrogen, stirring is started, the mixture is introduced into an active fluorine gas mixture prepared according to the method of the example 1 at the temperature of minus 10 ℃ for reaction for 15h at the pressure of 60mL/min, the reaction pressure is 2bar, the temperature is raised to 100 ℃ for vigorous stirring for 10h, the temperature of the reaction system is reduced to minus 60 ℃, then oxygen is introduced, an LED ultraviolet lamp (with the wavelength of 254 nm) with the power of 50W is started, hexafluoropropylene, 1, 4-hexafluoro-2-butene is introduced according to a certain proportion, during the period, controlling the mol ratio of oxygen, hexafluoropropylene and 1, 4-hexafluoro-2-butene to be 2.5:0.5:0.5, keeping the reaction pressure to be 1bar, keeping the ultraviolet lamp to irradiate for 10 hours, turning off the ultraviolet lamp, stopping introducing fluoroolefin monomer, continuing to introduce oxygen for 30 minutes, stopping, 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 6.25mol, preparing a diacyl end group polymer, finally turning on the ultraviolet lamp, carrying out fluorination treatment by adopting the active fluorine gas mixture prepared according to the method of the embodiment 1, wherein the temperature is 90 ℃ and the time is 20 hours, and obtaining double-end perfluorinated polyether 19 F-NMR spectrum analysis shows that the average molecular weight is about 5700Da, and the yield is about 78% calculated by the fluoroolefin monomer charge.
Example 7
Adding 27.5g (62.5 mmol) of bis (pentafluoropropionyloxypropyl) methylamine and 1.4g (9.0 mmol) of cesium fluoride into a 1.8L photocatalytic reaction kettle equipped with a mechanical stirring and a condenser, after 400mL of 1, 2-trifluoro-1, 2-trichloroethane and high-purity nitrogen are replaced twice, starting stirring, introducing 50mL/min of active fluorine gas mixture prepared according to the method of example 1 at room temperature for 15h, reacting at 2bar, stopping introducing active fluorine gas mixture, heating to 90 ℃ for 7h, reducing the temperature of the reaction system to-60 ℃, introducing 1.6L of difluoromethane, introducing oxygen and carbon dioxide mixture (the flow ratio of oxygen to carbon dioxide is 7:3), opening an LED ultraviolet lamp (wavelength 254 nm) with the power of 100W, introducing tetrafluoroethylene and vinylidene fluoride according to a certain proportion, controlling the reflux temperature of the condenser to 77 ℃, maintaining the molar ratio of 2.0:0 for 2.0:2 bar of tetrafluoroethylene and vinylidene fluoride at room temperature, maintaining the pressure of 2:0, stopping introducing fluorine gas mixture to the total fluorine gas mixture for about 20h, continuously introducing the total fluorine gas mixture into the ultraviolet polymerization lamp for 20h, and continuously recovering the total fluorine gas mixture after the ultraviolet polymerization is carried out, and the total fluorine gas mixture is continuously introduced into the ultraviolet lamp is continuously, the ultraviolet polymerization is carried out for 20h, the total fluorine gas is continuously, the total fluorine is continuously carried out, the total fluorine is recovered, the total fluorine is continuously, the ultraviolet light is continuously prepared by the method is continuously, and the method is continuously subjected to the method is subjected to the steps of 20, and the method is subjected to the method and the method is 20, after the method is subjected to 20, and the 19 F-NMR spectrum analysis shows that the average molecular weight is about 25200Da, and the yield is about 70% calculated by the fluoroolefin monomer charge.
Example 8
The double-end perfluoropolyethers prepared in examples 1 to 7 were taken as equal mass samples, combined and subjected to fraction separation by molecular distillation to obtain double-end perfluoropolyethers of different average molecular weights, the corresponding average molecular weights, viscosities, pour points were tested, and viscosity indexes were calculated, and the results are shown in table 1.
TABLE 1 average molecular weight, viscosity and pour point of double ended perfluoropolyethers
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical solution of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. A method of preparing a double ended perfluoropolyether, the method comprising:
(1) In the presence of metal fluoride, N, N-bis (perfluoroalkyl acyloxyalkyl) amine or bis (perfluoroalkyl acyloxyalkyl) alkylamine is fluorinated by an active fluorine source to obtain glycol amine fluoride; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride; the active fluorine source is obtained by ultraviolet irradiation of a fluorination reagent, wherein the fluorination reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas;
(2) Under the irradiation of ultraviolet light, the perfluorinated olefin monomer, the second fluorinated olefin monomer, the glycol amine fluoride and oxygen or oxygen carbon dioxide mixed gas are subjected to photo-oxidative polymerization to obtain a diacyl end group polymer; the photo-oxidative polymerization reaction conditions are as follows: the reaction temperature is between 70 ℃ below zero and 25 ℃ below zero, and the reaction pressure is between 0.5 and 4bar; the second fluoroolefin monomer is a C2-C4 fluoroolefin;
(3) Carrying out fluorination treatment on the diacyl end group polymer by adopting an active fluorine source at 50-120 ℃ to obtain double-end perfluoropolyether;
the N, N-bis (perfluoroalkyl acyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (pentafluoropropionyloxybutyl) amine, N-bis (trifluoroacetoxyethyl) amine, N-bis (trifluoroacetoxypropyl) amine or N, N-bis (trifluoroacetoxybutyl) amine; the bis (perfluoroalkyl acyloxyalkyl) alkylamine is selected from bis (pentafluoropropionyloxyethyl) methylamine, bis (pentafluoropropionyloxyethyl) ethylamine, bis (pentafluoropropionyloxyethyl) propylamine, bis (trifluoroacetoxyethyl) methylamine, bis (trifluoroacetoxyethyl) ethylamine, bis (trifluoroacetoxyethyl) propylamine, bis (pentafluoropropionyloxypropyl) methylamine, bis (pentafluoropropionyloxypropyl) ethylamine, bis (trifluoroacetoxypropyl) methylamine, bis (trifluoroacetoxypropyl) ethylamine, bis (pentafluoropropionyloxybutyl) methylamine, bis (pentafluoropropionyloxybutyl) ethylamine, bis (trifluoroacetoxybutyl) methylamine or bis (trifluoroacetoxybutyl) ethylamine;
the perfluorinated olefin monomer is selected from one or more than two of tetrafluoroethylene, hexafluoropropylene and hexafluorobutadiene;
the second fluoroolefin monomer is selected from vinylidene fluoride, trifluoroethylene, 3-trifluoropropene, 2, 3-tetrafluoropropene 1, 3-tetrafluoropropene, 1,2, 3-pentafluoropropene 1, 3-pentafluoropropene, 1, 4-hexafluoro-2-butene 1-chloro-3, 3-trifluoropropene, 2-chloro-3, 3-trifluoropropene, 1, 2-dichloro-3, 3-trifluoropropene 1-chloro-2, 3-tetrafluoropropene or 2-chloro-1, 4-one or two or more of hexafluoro-2-butene.
2. The method according to claim 1, wherein the volume ratio of oxygen to carbon dioxide in the oxygen-carbon dioxide mixture is [ 7-10 ]: 0-3 ].
3. The method according to claim 1, wherein the reaction temperature of the photo-oxidative polymerization is-60 ℃ to-40 ℃.
4. The method of claim 1, wherein the molar amount of glycol amine fluoride to total molar amount of monomers is 1: 50-350.
5. The method of claim 1, further comprising fractionally separating the resulting double-ended perfluoropolyether by molecular distillation to obtain double-ended perfluoropolyethers of different average molecular weights.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111672157.5A CN114395117B (en) | 2021-12-31 | 2021-12-31 | Double-end perfluoropolyether and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143589A (en) * | 1988-05-02 | 1992-09-01 | Ausimont S.R.L. | Perfluoropolyethers containing a halogen different from fluorine and having an acid end group |
| US5488181A (en) * | 1993-11-17 | 1996-01-30 | Ausimont S.P.A. | Process for preparing perfluoropolyethers |
| CN102341229A (en) * | 2009-03-03 | 2012-02-01 | 三菱丽阳株式会社 | Process for producing film |
| CN108440748A (en) * | 2018-04-09 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of high molecular weight carries the synthetic method of acyl fluorides group perfluoropolyether peroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ITMI20031915A1 (en) * | 2003-10-03 | 2005-04-04 | Solvay Solexis Spa | PROCESS FOR THE PREPARATION OF PERFLUOROPOLIETERS. |
| US20070161768A1 (en) * | 2004-01-30 | 2007-07-12 | Hidetoshi Odaka | Method for producing hydrolyzable silicon group-containing oxyalkylene polymer and curing composition thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5143589A (en) * | 1988-05-02 | 1992-09-01 | Ausimont S.R.L. | Perfluoropolyethers containing a halogen different from fluorine and having an acid end group |
| US5488181A (en) * | 1993-11-17 | 1996-01-30 | Ausimont S.P.A. | Process for preparing perfluoropolyethers |
| CN102341229A (en) * | 2009-03-03 | 2012-02-01 | 三菱丽阳株式会社 | Process for producing film |
| CN108440748A (en) * | 2018-04-09 | 2018-08-24 | 浙江巨化技术中心有限公司 | A kind of high molecular weight carries the synthetic method of acyl fluorides group perfluoropolyether peroxide |
Non-Patent Citations (1)
| Title |
|---|
| 光氧化法制备全氟聚醚酸工艺研究;张鸣等;《化工生产与技术》;第20卷(第4期);第13-16页 * |
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