CN114395119A - Binary copolymerization perfluoropolyether and preparation method thereof - Google Patents
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Abstract
The invention discloses binary copolymerization perfluoropolyether and a preparation method thereof. The structural formula of the disclosed binary copolymerization perfluoropolyether is shown as the formula (I); the preparation method comprises the following steps: under the conditions of anhydrous inert atmosphere and-50 to-30 ℃, initiating a hexafluoropropylene oxide monomer and a perfluorooxetane monomer to carry out polymerization reaction in a viscosity regulator by an initiator, and removing the viscosity regulator after the reaction is finished to obtain a polymer; the initiator is a perfluorinated diol metal salt solution or a perfluorinated glycol amine metal salt solution; and then, stabilizing the polymer at the temperature of 100-240 ℃ by adopting an active fluorine source to obtain binary copolymerization perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluorination reagent by ultraviolet light, and the fluorination reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas. The binary copolymerization perfluoropolyether has high viscosity index of more than 236, low pour point of below 68 ℃ and can meet the lubricating and sealing requirements under the extreme working conditions of wide temperature range and the like.
Description
Technical Field
The invention belongs to the technical field of perfluoropolyether, and particularly relates to binary copolymerization perfluoropolyether of hexafluoropropylene oxide and perfluorooxetane 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, two methods for preparing perfluoropolyether are mainly used, the first method is that perfluoroolefin is photo-oxidative polymerized to prepare perfluoropolyether, the method relates to a free radical polymerization mechanism, the reaction process at least involves the addition of oxygen and a central free radical, the chain growth of a perfluoroperoxy free radical, the chain growth of a perfluoroalkoxy radical, the degradation of a perfluoroperoxy radical to generate a perfluoroalkoxy free radical, the chain termination reaction of coupling of the perfluoroperoxy radical with the free radical, and the like, the process is complex and difficult to control, and the generated perfluoropolyether acyl fluoride has complex structure composition and changeable arrangement sequence and proportion of each group. The other is anion polymerization represented by hexafluoropropylene oxide, and the method has the advantages of simple process, safe and controllable process, stable structural composition of the perfluoropolyether acyl fluoride product, high yield and wide research. However, the K-type perfluoropolyether prepared by the existing anionic polymerization method has small viscosity index and high pour point, and the viscosity index of the K-type perfluoropolyethers of GPL 101-GPL 107 and other types is less than 150 according to the perfluoropolyether product data of DuPont in the United states, and the pour point can reach up to-30 ℃ along with the increase of the average molecular weight. Furthermore, the performance and physical parameters of K-type perfluoropolyether are reported in detail by David et al, American aerospace company, and it is clearly indicated that K-type perfluoropolyether having an average molecular weight of 3700 has a viscosity index of only 113 and a pour point of-43 ℃ (A S L E transformations, 28(1), 40-46). The organic fluorine industry, 2008 (1): 31-34 and journal of tribology, 2005, 25 (6): 597-602 reports the performance and parameters of perfluoropolyether, and the related results are basically consistent. While the relatively small (< 150) viscosity index and high pour point make it difficult for type K perfluoropolyethers to meet the use requirements of a lubricated seal over a wide temperature range. Therefore, the development of novel perfluoropolyethers having high viscosity index, low pour point, safe process and low product cost is urgently needed.
Disclosure of Invention
Aiming at the defects or shortcomings of the prior art, the invention provides binary copolymerized perfluoropolyether.
The structural formula of the binary copolymerized perfluoropolyether is shown as the formula (I):
wherein: rfIs composed of
m is 1,2 or 3, n is 1,2 or 3; the molar ratio of hexafluoropropylene oxide to perfluorooxetane structural units is (p + q): r + s, and (p + q): r + s): 1: 6-30, wherein p, q, r and s are all larger than 0; a is CF3-or CF3CF2-; b is CF3-or CF3CF2-。
The invention also provides a preparation method of the binary copolymerization perfluoropolyether. The preparation method comprises the following steps:
(1) under the conditions of anhydrous inert atmosphere and-50 to-30 ℃, initiating hexafluoropropylene oxide monomer and perfluorooxetane monomer to carry out polymerization reaction in a viscosity regulator by an initiatorRemoving the viscosity regulator to obtain a polymer; the initiator is perfluorodiglycol metal salt
Solutions or metal salts of perfluorodialolamine
A solution, M is K, Cs, Rb or Ag, M is 1,2 or 3, n is 1,2 or 3; the viscosity regulator is difluorochloromethane, difluorodichloromethane, pentafluoroethane, hexafluoropropylene or heptafluoropropane;
(2) the method comprises the following steps of adopting an active fluorine source to stabilize the polymer at the temperature of 100-240 ℃ to obtain binary copolymerization perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluorination reagent with ultraviolet light, and the fluorination reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas.
Optionally, the reaction time of the step (1) is 11.5-12.5 h.
Optionally, the stabilizing treatment in the step (2) is carried out for 5-30 h.
The preparation method further comprises the step of carrying out fraction segmentation on the obtained binary copolymerization perfluoropolyether by adopting molecular distillation to obtain the binary copolymerization perfluoropolyethers with different average molecular weights.
Optionally, the preparation method of the initiator comprises the following steps: in the atmosphere of fluorine gas, perfluoro-carboxyl diglycol diester or N, N-bis (perfluoroalkyl acyloxy alkyl) amine reacts with metal fluoride at a low temperature range of-30 ℃ to-10 ℃, and then reacts at a high temperature range of 50 ℃ to 80 ℃ in polar aprotic solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether or tetraethylene glycol diethyl ether to obtain perfluoro-diglycol metal salts or perfluoro-glycol amine metal salts with different concentrations; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride.
Optionally, the reaction time in the low-temperature region is 10-15 h; the reaction time in the high-temperature zone is 8-15 h.
Optionally, the perfluorocarboxylic diglycol diester is selected from diethylene glycol pentafluoride propionate diester, triethylene glycol trifluoroacetate diester or tetraethylene glycol trifluoroacetate diester; the N, N-bis (perfluoroalkanoyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (trifluoroacetyloxyethyl) amine or N, N-bis (trifluoroacetyloxybutyl) amine; the metal fluoride is cesium fluoride; the reaction solvent is tetraethylene glycol dimethyl ether or tetraethylene glycol diethyl ether.
Optionally, the ratio of the molar amount of the initiator to the total molar amount of the monomers is 1:30 to 750 parts.
Optionally, the viscosity regulator in the step (1) is hexafluoropropylene; the molar weight of the viscosity regulator is 0.3-3.0 times of the total molar weight of the monomers.
Compared with the prior K-type perfluoropolyether, the novel binary copolymerization perfluoropolyether has the advantages that the specific viscosity index is remarkably improved and can reach over 236, the pour point is remarkably reduced and is lower than-68 ℃, and the lubricating requirements under the extreme working conditions of wide temperature range and the like can be met; meanwhile, the preparation method of the binary copolymerization perfluoropolyether has the advantages of wide initiator source, high catalytic efficiency and safe and stable reaction process, and can realize the modulation of the performance of the perfluoropolyether by regulating and controlling molecular structural units, thereby providing a new technical thought for the modification of the K-type perfluoropolyether.
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 polymerization products in the following examples were measured and analyzed by a gel permeation chromatograph, model GPC-50, manufactured by PL corporation, UK; GPC chromatographic conditions: the mobile phase is 1,2, 2-trifluoro-1, 1, 2-trichloroethane, and is degassed in vacuum by a 0.45 mu m microporous membrane in advance, and then is degassed by ultrasonic, the flow rate is 1.0mL/min, and the temperature of a column incubator is 40 ℃. The viscosity of the polymerization product was measured using a viscometer model MCR302 of Olympa 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 polymerization product is determined by using the national standard GB/T3535-2006.
Example 1:
20mL of initiator (CsOCF) was added to the polymerization reactor under an anhydrous nitrogen atmosphere2CF2OCF2CF2OCF2CF2OCs content of 10mmol), reducing the temperature of the reaction system to-35 ℃, starting stirring, adding 13.5g (0.09mol) of hexafluoropropylene into the reaction kettle, then introducing dried perfluoroepoxide monomer (molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:15) with purity of more than 99.9 percent into the reaction kettle to totally 49.8g (0.3mol), and reacting for 12 hours after the addition is finished; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing hexafluoropropylene, then transferring the polymer to a fluorination reaction kettle, and carrying out stabilization treatment by adopting active fluorine gas mixed gas at the temperature of 200 ℃ for 20 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 2.2g (5.0mmol) of triethylene glycol diester pentafluoropropionate and 1.67g (11.0mmol) of cesium fluoride into a high-pressure reaction kettle with a magnetic stirring and a condenser, replacing the materials with nitrogen twice, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at 50ml/min at the temperature of minus 20 ℃ for reaction for 12 hours, reacting at the pressure of 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, sucking 10ml of dried tetraethylene glycol dimethyl ether, heating to 50 ℃ for reaction for 15 hours, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted cesium fluoride, and preparing the cesium fluoride metal salt CsOCF2CF2OCF2CF2OCF2CF2OCs solution.
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:
24mL of an initiator (KOCF) was added to the polymerization reactor under an anhydrous nitrogen atmosphere2CF2OCF2CF2OK content 10mmol), reducing the temperature of the reaction system to-45 ℃, starting stirring, adding 103.8g (1.20mol) of difluorochloromethane into the reaction kettle, then introducing dried perfluoroepoxide monomer (the molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:10) with the purity of more than 99.9 percent into the reaction kettle to totally 132.8g (0.8mol), and reacting for 12 hours after the addition is finished; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing the monochlorodifluoromethane, then transferring the polymer to a fluorination reaction kettle, and carrying out stabilization treatment by adopting active nitrogen trifluoride at the temperature of 100 ℃ for 30 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 2.0g (5.0mmol) of diethylene glycol pentafluoride dipropionate and 0.58g (10.0mmol) of potassium fluoride into a high-pressure reaction kettle provided with a magnetic stirring condenser, replacing twice with nitrogen, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at-30 ℃ at 50ml/min for reaction for 15h, wherein the reaction pressure is 2bar, vacuumizing the reaction kettle for 0.5h at room temperature, sucking 12ml of dried tetraethylene glycol diethyl ether, heating to 80 ℃ for reaction for 8h, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted potassium fluoride, and preparing the perfluorodiglycol metal potassium salt KOCF2CF2OCF2CF2OK solution.
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, 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 1000W, irradiating by ultraviolet light for 30s, and transferring the activated light to an active nitrogen trifluoride storage tank for later use after activation.
Example 3:
this example differs from example 1 in that: 10mL of initiator I3 (AgOCF) was added to the polymerization kettle under an anhydrous nitrogen atmosphere2CF2OCF2CF2OCF2CF2OCF2CF2OAg content of 5mmol), reducing the temperature of the reaction system to-50 ℃, starting stirring, adding 150g (1.25mol) of pentafluoroethane (HFC-125) into a reaction kettle, then introducing dried perfluoroepoxide monomer with purity of more than 99.9% (the molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:30) into the reaction kettle to count 207.5g (1.25mol), and reacting for 12 hours after the addition is finished; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing HFC-125, transferring the polymer to a fluorination reaction kettle, and stabilizing by adopting active fluorine gas mixed gas at the temperature of 150 ℃ for 20 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 1.9g (5.0mmol) of tetraethylene glycol triacetate trifluoroacetate and 1.59g (12.5mmol) of silver fluoride into a high-pressure reaction kettle provided with a magnetic stirring condenser, replacing the materials with nitrogen twice, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at 50ml/min at the temperature of minus 10 ℃ for reaction for 10 hours at the reaction pressure of 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, sucking 20ml of dried triethylene glycol diethyl ether, heating to 50 ℃ for reaction for 15 hours, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted silver fluoride, and preparing the silver perfluoroacetal silver salt AgOCF2CF2OCF2CF2OCF2CF2OCF2CF2OAg solution.
Example 4:
adding 5mL of initiator into the polymerization kettle under the anhydrous nitrogen atmosphere condition
Content 2.5mmol), reducing the temperature of the reaction system to-32 ℃, starting stirring, adding 169.2g (1.13mol) of hexafluoropropylene into the reaction kettle, then introducing dried perfluoroepoxide monomer (molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:6) with purity of more than 99.9 percent, totaling 311.3g (1.88mol), and reacting for 12 hours after the end of the addition; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing hexafluoropropylene, then transferring the polymer to a fluorination reaction kettle, and carrying out stabilization treatment by adopting active carbonyl fluoride mixed gas at the temperature of 180 ℃ for 15 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 2.0g (5.0mmol) of N, N-bis (pentafluoropropionyloxyethyl) amine and 1.67g (11.0mmol) of cesium fluoride into a high-pressure reaction kettle with a magnetic stirring and a condenser, replacing the nitrogen for two times, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at 50ml/min at the temperature of-20 ℃ for reaction for 12 hours, reacting at the pressure of 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, sucking 10ml of dry tetraethyleneglycol dimethyl ether, heating to 60 ℃ for reaction for 9 hours, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted cesium fluoride, and preparing the perfluoroglycol amine cesium metal salt
And (3) solution.
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 5:
adding 24mL of initiator into the polymerization kettle under the anhydrous nitrogen atmosphere condition
Content 10mmol), reducing the temperature of the reaction system to-45 ℃, starting stirring, adding 340.0g (2.0mol) of heptafluoropropane (HFC-227ea) into a reaction kettle, introducing dried perfluoroepoxide monomer (the molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:20) with the purity of more than 99.9 percent to totally 166.0g (1.0mol), and reacting for 12 hours after the addition is finished; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing HFC-227ea, transferring the polymer to a fluorination reaction kettle, and stabilizing by adopting active fluorine gas mixed gas at the temperature of 150 ℃ for 20 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 2.1g (5.0mmol) of N, N-bis (pentafluoropropionyloxypropyl) amine and 1.82g (12.0mmol) of cesium fluoride into a high-pressure reaction kettle with a magnetic stirring and a condenser, replacing the nitrogen for two times, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at 50ml/min at-30 ℃ for reaction for 15 hours at the reaction pressure of 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, sucking 12ml of dried triethylene glycol dimethyl ether, heating to 70 ℃ for reaction for 8 hours, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted cesium fluoride, and preparing the perfluoro-glycol amine cesium metal salt
And (3) solution.
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 6:
adding 18mL of initiator I7 (under the condition of anhydrous nitrogen atmosphere)
Content of 5mmol), reducing the temperature of the reaction system to-40 DEG CStarting stirring, adding 270.0g (2.25mol) of difluoro dichloromethane into a reaction kettle, then introducing 124.5g (0.75mol) of dried perfluoro epoxide monomer (the molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:12) with the purity of more than 99.9 percent, and reacting for 12 hours after the addition is finished; after the reaction is finished, slowly raising the temperature of the reaction kettle to 50 ℃, removing difluorodichloromethane, then transferring the polymer to a fluorination reaction kettle, and carrying out stabilization treatment by adopting active fluorine gas mixed gas at the temperature of 240 ℃ for 5 hours to obtain the stable binary copolymerization perfluoropolyether.
The preparation method of the initiator in the embodiment comprises the following steps: adding 1.8g (5.0mmol) of N, N-bis (trifluoroacetoxybutyl) amine and 1.41g (13.5mmol) of rubidium fluoride into a high-pressure reaction kettle with a magnetic stirring and a condenser, replacing the N with nitrogen twice, introducing 30% fluorine gas/nitrogen (V/V) mixed gas at 50ml/min at the temperature of minus 10 ℃ for reaction for 10 hours at the reaction pressure of 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, then sucking 18ml of dried tetraethyleneglycol dimethyl ether, heating to 50 ℃ for reaction for 15 hours, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted rubidium fluoride, and preparing the perfluoro-glycol amine cesium metal salt
And (3) solution.
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 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, 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 1000W, irradiating by ultraviolet light for 30s, and transferring the activated light to an active nitrogen trifluoride storage tank for later use after activation.
Example 7:
the binary copolymerized perfluoropolyethers prepared in examples 1 to 6 were subjected to fraction segmentation by molecular distillation, the binary copolymerized perfluoropolyethers having different average molecular weights in each example were taken, the corresponding average molecular weights, viscosities, and pour points were measured, and viscosity indexes were calculated, the results of which are shown in table 1.
TABLE 1 average molecular weight, viscosity, pour Point of binary perfluoropolyethers
Compared with the prior K-type perfluoropolyether, the binary copolymerization perfluoropolyether provided by the invention has the advantages that the viscosity index is obviously improved, the pour point is obviously reduced, the comprehensive performance is more excellent, and the lubricating use requirements under severe conditions such as a wide temperature range can be met.
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 (10)
1. The binary copolymerized perfluoropolyether is characterized in that the structural formula of the binary copolymerized perfluoropolyether is shown as the formula (I):
wherein: rfIs composed of
m is 1,2 or 3, n is 1,2 or 3; the molar ratio of hexafluoropropylene oxide to perfluorooxetane structural units is (p + q): r + s, and (p + q): r + s): 1: 6-30, wherein p, q, r and s are all larger than 0; a is CF3-or CF3CF2-; b is CF3-or CF3CF2-。
2. A process for preparing a binary copolymerized perfluoropolyether according to claim 1, comprising:
(1) in the absence of waterInitiating a polymerization reaction of a hexafluoropropylene oxide monomer and a perfluorooxetane monomer in a viscosity regulator by an initiator under an inert atmosphere at a temperature of-50 ℃ to-30 ℃, and removing the viscosity regulator after the reaction is finished to obtain a polymer; the initiator is perfluorodiglycol metal salt
Solutions or metal salts of perfluorodialolamine
A solution, M is K, Cs, Rb or Ag, M is 1,2 or 3, n is 1,2 or 3; the viscosity regulator is difluorochloromethane, difluorodichloromethane, pentafluoroethane, hexafluoropropylene or heptafluoropropane;
(2) the method comprises the following steps of adopting an active fluorine source to stabilize the polymer at the temperature of 100-240 ℃ to obtain binary copolymerization perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluorination reagent with ultraviolet light, and the fluorination reagent is a mixed gas of fluorine gas, nitrogen trifluoride or carbonyl fluoride and an inert gas.
3. The method according to claim 2, wherein the reaction time of the step (1) is 11.5 to 12.5 hours.
4. The method according to claim 2, wherein the stabilizing treatment in the step (2) is carried out for 5 to 30 hours.
5. The method of claim 2, further comprising fractionating the resultant binary copoly (perfluoropolyether) by molecular distillation to obtain binary copoly (perfluoropolyethers) of different average molecular weights.
6. The method of claim 2, wherein the initiator is prepared by a method comprising the steps of:
in the atmosphere of fluorine gas, perfluoro-carboxyl diglycol diester or N, N-bis (perfluoroalkyl acyloxy alkyl) amine reacts with metal fluoride at a low temperature range of-30 ℃ to-10 ℃, and then reacts at a high temperature range of 50 ℃ to 80 ℃ in polar aprotic solvents such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol diethyl ether or tetraethylene glycol diethyl ether to obtain perfluoro-diglycol metal salts or perfluoro-glycol amine metal salts with different concentrations; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride.
7. The preparation method of claim 6, wherein the reaction time in the low temperature region is 10-15 h; the reaction time in the high-temperature zone is 8-15 h.
8. The method of claim 6, wherein the perfluorocarboxylic acid diester is selected from the group consisting of diethylene glycol pentafluoride propionate, triethylene glycol trifluoroacetate, and tetraethylene glycol trifluoroacetate; the N, N-bis (perfluoroalkanoyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (trifluoroacetyloxyethyl) amine or N, N-bis (trifluoroacetyloxybutyl) amine; the metal fluoride is cesium fluoride; the reaction solvent is tetraethylene glycol dimethyl ether or tetraethylene glycol diethyl ether.
9. The method of claim 2, wherein the ratio of the molar amount of the initiator to the total molar amount of the monomers is from 1:30 to 750 parts.
10. The method according to claim 2, wherein the viscosity modifier in the step (1) is hexafluoropropylene; the molar weight of the viscosity regulator is 0.3-3.0 times of the total molar weight of the monomers.
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2021
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| CN104513390A (en) * | 2013-12-24 | 2015-04-15 | 东莞市长安东阳光铝业研发有限公司 | Method for preparing hexafluoropropylene oxide oligomer |
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| CN105175713A (en) * | 2015-10-19 | 2015-12-23 | 北京莱诺泰克科技有限公司 | Perfluoropolyether silane, preparation method of perfluoropolyether silane and application of perfluoropolyether silane |
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