CN114395119B - 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 formula (I); the disclosed preparation method comprises the following steps: under the conditions of anhydrous inert atmosphere and minus 50 ℃ to minus 30 ℃, initiating a polymerization reaction of hexafluoropropylene oxide monomers and perfluorooxetane monomers 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 perfluoro-glycol metal salt solution or perfluoro-glycol amine metal salt solution; and then stabilizing the polymer by adopting an active fluorine source at the temperature of 100-240 ℃ to obtain binary copolymerized perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluoridation reagent by ultraviolet light, and the fluoridation reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas. The binary copolymerization perfluoropolyether of the invention has high viscosity index, more than 236, low pour point and less than minus 68 ℃, and can meet the lubrication and sealing requirements under the limit working conditions of wide temperature range and the like.
Description
Technical Field
The invention belongs to the technical field of perfluoropolyethers, and particularly relates to binary copolymerization perfluoropolyether of hexafluoropropylene oxide and perfluorooxetane 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 preparation methods of perfluoropolyether mainly exist, the first method is that perfluoroolefin is subjected to photo-oxidative polymerization to prepare the perfluoropolyether, the method relates to a free radical polymerization mechanism, the reaction process at least relates to addition of oxygen and a central free radical, chain growth of perfluoro peroxy free radical, chain growth of perfluoro alkoxy, perfluoro peroxy free radical degradation to generate perfluoro alkoxy free radical, perfluoro peroxy free radical coupling chain termination reaction and the like, the process is complex and difficult to control, and the generated perfluoro polyether acyl fluoride has complex structure composition, and the arrangement sequence and proportion of each group are changeable. 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 perfluoro polyether 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 perfluoropolyether of GPL 101-GPL 107 and other types is less than 150 according to the data of the perfluoropolyether products of DuPont company in the United states, and the pour point of the K-type perfluoropolyether is up to-30 ℃ along with the increase of the average molecular weight. In addition, the U.S. aerospace company David et al report in detail the performance and physical parameters of the K-type perfluoropolyether, and clearly indicate that the K-type perfluoropolyether having an average molecular weight of 3700 has a viscosity index of only 113 and a pour point of up to-43 ℃ (A S L E Transactions,28 (1), 40-46). Literature organofluorine industry, 2008 (1): 31-34, tribology journal, 2005, 25 (6): 597-602 also reports about the performance and parameters of the perfluoropolyether, and the relevant results are basically consistent. While the relatively small (< 150) viscosity index and high pour point make it difficult for K-perfluoropolyethers to meet the use requirements of lubrication seals under wide temperature range conditions. Therefore, there is an urgent need to develop novel perfluoropolyethers with high viscosity index, low pour point, process safety, and low product cost.
Disclosure of Invention
Aiming at the defects or shortcomings in the prior art, the invention provides binary copolymerization perfluoropolyether.
The structural formula of the binary copolymerization perfluoropolyether provided by the invention is shown as the formula (I):
wherein: r is R f Is that
m=1, 2 or 3, n=1, 2 or 3; the molar ratio of hexafluoropropylene oxide, perfluorooxetane building blocks is (p+q): (r+s), and (p+q): (r+s) =1: 6 to 30, and p, q, r, s are all more than 0; a is CF 3 -or CF 3 CF 2 -; b is CF 3 -or CF 3 CF 2 -。
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 minus 50 ℃ to minus 30 ℃, initiating a polymerization reaction of hexafluoropropylene oxide monomers and perfluorooxetane monomers in a viscosity regulator by an initiator, and removing the viscosity regulator after the reaction is finished to obtain a polymer; the initiator is perfluoro-glycol metal salt
Solution or perfluoro-glycol amine metal salt
Solution, M is K, cs, rb or Ag, m=1, 2 or 3, n=1, 2 or 3; the viscosity modifier is difluoro chloromethane, difluoro dichloromethane, pentafluoroethane, hexafluoropropylene or heptafluoropropane;
(2) And (3) stabilizing the polymer at 100-240 ℃ by adopting an active fluorine source to obtain binary copolymerized perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluoridation reagent by ultraviolet light, and the fluoridation reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas.
Optionally, the reaction time of the step (1) is 11.5-12.5h.
Optionally, the stabilizing treatment in the step (2) is carried out for 5-30h.
The preparation method further comprises the step of carrying out fraction segmentation on the obtained binary copolymerization perfluoropolyether by molecular distillation to obtain binary copolymerization perfluoropolyether with different average molecular weights.
Optionally, the preparation method of the initiator comprises the following steps: in the atmosphere of fluorine, perfluoro carboxyl glycol diester or N, N-bis (perfluoroalkyl acyloxyalkyl) amine reacts with metal fluoride at the low temperature range of minus 30 ℃ to minus 10 ℃, and then reacts 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 and the like at the high temperature range of 50 ℃ to 80 ℃ to obtain perfluoro glycol metal salt or perfluoro glycol amine metal salt 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 zone is 10-15 h; the reaction time in the high temperature interval is 8-15 h.
Optionally, the perfluorocarboxyl diol diester is selected from diethylene glycol pentafluoride diester, triethylene glycol trifluoroacetate diester or tetraethylene glycol trifluoroacetate diester; the N, N-bis (perfluoroalkyl acyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (trifluoroacetoxyethyl) amine or N, N-bis (trifluoroacetoxybutyl) amine; the metal fluoride is cesium fluoride; the reaction solvent is tetraethylene glycol dimethyl ether or tetraethylene glycol diethyl ether.
Alternatively, the molar amount of initiator to total molar amount of monomer ratio is 1: 30-750.
Optionally, the viscosity modifier in step (1) is hexafluoropropylene; the molar amount of the viscosity modifier is 0.3 to 3.0 times the total molar amount of the monomers.
Compared with the prior K-type perfluoropolyether, the novel binary copolymerization perfluoropolyether has obviously improved specific viscosity index, can reach more than 236, obviously reduces pour point, is lower than-68 ℃, and can meet the lubrication requirement under the limit working conditions of wide temperature range and the like; meanwhile, the preparation method of the binary copolymerization perfluoropolyether provided by the invention has the advantages of wide initiator source, high catalytic efficiency, safe and stable reaction process, and can realize the modulation of the performance of the perfluoropolyether through the regulation and control of a molecular structural unit, thereby providing a new technical idea for the modification of K-type perfluoropolyether.
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 polymerization products in the following examples was measured and analyzed by using a gel permeation chromatograph, GPC-50, of PL company, england; GPC chromatographic conditions: the mobile phase is 1, 2-trifluoro-1, 2-trichloroethane, which is vacuum degassed by a microporous filter membrane with the thickness of 0.45 mu m in advance, and then is ultrasonically degassed at the flow rate of 1.0mL/min, and the temperature of a column temperature box is 40 ℃. The viscosity of the polymerization product was measured using an Austria An Dongpa Co., ltd., MCR302 type viscometer under the conditions: the temperature rising rate is 5 ℃/min, the test temperature range is 20-120 ℃, and the viscosity index of the sample is calculated by adopting national standard GB/T1995-1998. The pour point of the polymerization product is measured by national standard GB/T3535-2006.
Example 1:
under the anhydrous nitrogen atmosphere, 20mL of initiator (CsOCF) was added to the polymerization reactor 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 After the temperature of the reaction system is reduced to minus 35 ℃, stirring is started, 13.5g (0.09 mol) of hexafluoropropylene is added into a reaction kettle, 49.8g (0.3 mol) of perfluoro epoxide monomer (molar ratio of hexafluoropropylene to perfluorooxetane is 1:15) with purity of more than 99.9 percent after drying treatment is added, and the reaction is carried out for 12 hours after the addition; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃ to remove hexafluoropropylene, then the polymer is transferred to a fluorination reaction kettle, and the stabilization treatment is carried out by adopting active fluorine gas mixture, wherein the temperature is 200 ℃ and the time is 20 hours, so that the stable binary copolymerization perfluoropolyether is obtained.
The preparation method of the initiator comprises the following steps: 2.2g (5.0 mmol) of triethylene glycol diester of pentafluoropropionate and 1.67g (11.0 mmol) of cesium fluoride are added into a high-pressure reaction kettle with a magnetic stirring condenser, nitrogen is substituted twice, 30% of fluorine gas/nitrogen (V/V) mixed gas is introduced at 50ml/min at-20 ℃ for reaction for 12h, the reaction pressure is 2bar, the reaction kettle is vacuumized for 0.5h at room temperature, 10ml of dry tetraethylene glycol dimethyl ether is sucked, the temperature is raised to 50 ℃ for reaction for 15h, after the reaction is finished, the mixture is cooled to room temperature, unreacted cesium fluoride is centrifugally removed, and the perfluoro glycol cesium metal salt CsOCF is prepared 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCs solution.
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:
24mL of initiator (KOCF) was added to the polymerization reactor under an anhydrous nitrogen atmosphere 2 CF 2 OCF 2 CF 2 OK content 10 mmol), lowering the temperature of the reaction system to-45 ℃, starting stirring, adding 103.8g (1.20 mol) of difluoro chloromethane into the reaction kettle, and then introducing perfluoro epoxy with purity of more than 99.9% after drying treatment132.8g (0.8 mol) of the monomer (molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:10) is added, and the reaction is carried out for 12 hours after the addition; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃, difluoromethane chloride is removed, then the polymer is transferred to a fluorination reaction kettle, and stabilization treatment is carried out by adopting active nitrogen trifluoride, wherein the temperature is 100 ℃, and the time is 30 hours, so that the stable binary copolymerization perfluorinated polyether is obtained.
The preparation method of the initiator comprises the following steps: adding 2.0g (5.0 mmol) of diethylene glycol diester of pentafluoropropionate and 0.58g (10.0 mmol) of potassium fluoride into a high-pressure reaction kettle with a magnetic stirring condenser, replacing nitrogen twice, introducing 30% fluorine/nitrogen (V/V) mixed gas at 50ml/min at-30 ℃ for reaction for 15h, reacting at 2bar, vacuumizing the reaction kettle at room temperature for 0.5h, sucking 12ml of dry 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 perfluoroethylene glycol metal potassium salt KOCF 2 CF 2 OCF 2 CF 2 OK solution.
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 1000W, irradiating ultraviolet light for 30s, and transferring the activated product to an active nitrogen trifluoride storage tank for standby.
Example 3:
this embodiment differs from embodiment 1 in that: 10mL of initiator I3 (AgOCF) was added to the polymerization vessel under anhydrous nitrogen atmosphere 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OAg content 5 mmol), lowering the temperature of the reaction system to-50deg.C, stirring, adding 150g (1.25 mol) of pentafluoroethane (HFC-125) into the reaction kettle, and introducing the dried perfluoroepoxide monomer (hexafluoropropylene oxide and perfluorooxy) with purity of more than 99.9%The molar ratio of the heterocycle butane is 1:30, and the total is 207.5g (1.25 mol), and the reaction is carried out for 12 hours after the addition is finished; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃ to remove HFC-125, then the polymer is transferred to a fluorination reaction kettle, and the stabilization treatment is carried out by adopting active fluorine gas mixture, wherein the temperature is 150 ℃ and the time is 20 hours, so that the stable binary copolymerization perfluoropolyether is obtained.
The preparation method of the initiator comprises the following steps: adding 1.9g (5.0 mmol) of triethylene glycol diester of trifluoroacetic acid and 1.59g (12.5 mmol) of silver fluoride into a high-pressure reaction kettle with a magnetic stirring condenser, replacing nitrogen twice, introducing 30% fluorine/nitrogen (V/V) mixed gas at 50ml/min at-10 ℃ for reaction for 10h, reacting at 2bar, vacuumizing the reaction kettle at room temperature for 0.5h, sucking 20ml of dry triethylene glycol diethyl ether, heating to 50 ℃ for reaction for 15h, cooling to room temperature after the reaction is finished, centrifuging to remove unreacted silver fluoride, and preparing the perfluorodiol metallic silver salt AgOCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 2 CF 2 OAg solution.
Example 4:
under the anhydrous nitrogen atmosphere condition, 5mL of initiator is added into a polymerization reaction kettle
After the temperature of the reaction system is reduced to minus 32 ℃ and the reaction system is cooled to 2.5mmol, 169.2g (1.13 mol) of hexafluoropropylene is added into a reaction kettle, 311.3g (1.88 mol) of perfluoro epoxide monomer (molar ratio of hexafluoropropylene to perfluorooxetane is 1:6) with purity of more than 99.9 percent after drying treatment is added into the reaction kettle, and the reaction is carried out for 12 hours after the addition; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃ to remove hexafluoropropylene, then the polymer is transferred to a fluorination reaction kettle, and the stabilization treatment is carried out by adopting active carbonyl fluoride mixed gas, wherein the temperature is 180 ℃ and the time is 15 hours, so that the stable binary copolymerization perfluoropolyether is obtained.
The preparation method of the initiator comprises the following steps: adding N, N-bis (pentafluoropropioyloxy) into a high-pressure reaction kettle with magnetic stirring and a condenser2.0g (5.0 mmol) of ethyl amine and 1.67g (11.0 mmol) of cesium fluoride, after nitrogen replacement is carried out twice, 30 percent of fluorine gas/nitrogen gas (V/V) mixed gas is introduced at 50ml/min for reaction for 12 hours at the temperature of minus 20 ℃, the reaction pressure is 2bar, the reaction kettle is vacuumized for 0.5 hour at the room temperature, then 10ml of dry tetraethyleneglycol dimethyl ether is sucked, the temperature is increased to 60 ℃ for reaction for 9 hours, after the reaction is finished, the temperature is cooled to the room temperature, unreacted cesium fluoride is removed centrifugally, and the perfluoroglycol amine metal cesium salt is prepared
A solution.
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 5:
under the anhydrous nitrogen atmosphere condition, 24mL of initiator is added into a polymerization reaction kettle
After the temperature of the reaction system is reduced to-45 ℃, starting stirring, adding 340.0g (2.0 mol) of heptafluoropropane (HFC-227 ea) into a reaction kettle, and then introducing 166.0g (1.0 mol) of dried perfluoroepoxide monomer (the molar ratio of hexafluoropropylene oxide to perfluorooxetane is 1:20) with the purity of more than 99.9%, wherein the reaction kettle is reacted for 12 hours; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃ to remove HFC-227ea, then the polymer is transferred to a fluorination reaction kettle, and the stabilization treatment is carried out by adopting active fluorine gas mixture, wherein the temperature is 150 ℃ and the time is 20 hours, so that the stable binary copolymerization perfluoropolyether is obtained.
The preparation method of the initiator comprises the following steps: into a high-pressure reaction vessel equipped with a magnetic stirrer and a condenser, 2.1g (5.0 mmol) of N, N-bis (pentafluoropropiooxypropyl) amine and 1.82g (12.0 mmol) of cesium fluoride were charged) After nitrogen is replaced twice, introducing 30% fluorine/nitrogen (V/V) mixed gas at 50ml/min at minus 30 ℃ for reaction for 15 hours, the reaction pressure is 2bar, vacuumizing the reaction kettle for 0.5 hour at room temperature, then sucking 12ml of dry 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 obtaining the perfluoro-glycol amine metal cesium salt
A solution.
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 6:
under the anhydrous nitrogen atmosphere, 18mL of initiator I7 is added into a polymerization reaction kettle
After the temperature of the reaction system is reduced to minus 40 ℃, stirring is started, 270.0g (2.25 mol) of difluoro methylene dichloride is added into a reaction kettle, 124.5g (0.75 mol) of perfluoro epoxide monomer (molar ratio of hexafluoroepoxypropane to perfluoro oxetane is 1:12) with purity higher than 99.9 percent after drying treatment is introduced, and the reaction is carried out for 12 hours after the addition; after the reaction is finished, the temperature of the reaction kettle is slowly increased to 50 ℃, difluoro methylene dichloride is removed, then the polymer is transferred to a fluorination reaction kettle, and stabilization treatment is carried out by adopting active fluorine gas mixture, wherein the temperature is 240 ℃ and the time is 5 hours, so that the stable binary copolymerization perfluoropolyether is obtained.
The preparation method of the initiator comprises the following steps: 1.8g (5.0 mmol) of N, N-bis (trifluoroacetoxybutyl) amine and 1.41g (13.5 mmol) of rubidium fluoride were charged into a high-pressure reaction vessel equipped with a magnetic stirrer and a condenser, and after two nitrogen substitutions, 30% of fluorine gas was introduced at-10℃at 50ml/minNitrogen (V/V) mixed gas is reacted for 10 hours at the reaction pressure of 2bar, then the reaction kettle is vacuumized for 0.5 hour under the condition of room temperature, then 18ml of dry tetraethyleneglycol dimethyl ether is sucked in, the temperature is raised to 50 ℃ for reaction for 15 hours, after the reaction is finished, the mixture is cooled to the room temperature, unreacted rubidium fluoride is removed by centrifugation, and the perfluoro-dialcohol metal cesium salt is prepared
A solution.
The preparation method of the active fluorine gas mixture 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 1000W, irradiating ultraviolet light for 30s, and transferring the activated product to an active nitrogen trifluoride storage tank for standby.
Example 7:
the binary copolymerized perfluoropolyethers prepared in examples 1 to 6 were separated by molecular distillation, and the binary copolymerized perfluoropolyethers having different average molecular weights in each example were measured for their respective average molecular weights, viscosities, pour points, and viscosity indexes were calculated, and the results are shown in table 1.
TABLE 1 average molecular weight, viscosity and pour Point of binary perfluoropolyethers
Compared with the existing K-type perfluoropolyether, the viscosity index of the binary copolymerization perfluoropolyether provided by the invention 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 wide temperature range can be met.
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 (10)
1. The binary copolymerization perfluoropolyether is characterized in that the structural formula of the binary copolymerization perfluoropolyether is shown as the formula (I):
wherein: r is R f Is that
m=1, 2 or 3, n=1, 2 or 3; the molar ratio of hexafluoropropylene oxide, perfluorooxetane building blocks is (p+q): (r+s), and (p+q): (r+s) =1: 6 to 30, and p, q, r, s are all more than 0; a is CF 3 -or CF 3 CF 2 -; b is CF 3 -or CF 3 CF 2 -。
2. A process for the preparation of a binary copolymerized perfluoropolyether as claimed in claim 1, characterized in that it comprises:
(1) Under the conditions of anhydrous inert atmosphere and minus 50 ℃ to minus 30 ℃, initiating a polymerization reaction of hexafluoropropylene oxide monomers and perfluorooxetane monomers in a viscosity regulator by an initiator, and removing the viscosity regulator after the reaction is finished to obtain a polymer; the initiator is perfluoro-glycol metal salt
Solution or perfluoro-glycol amine metal salt
Solution, M is K, cs, rb or Ag, m=1, 2 or 3, n=1, 2 or 3; the viscosity modifier is difluoro chloromethane, difluoro dichloromethane, pentafluoroethane, hexafluoropropylene or heptafluoropropane;
(2) And (3) stabilizing the polymer at 100-240 ℃ by adopting an active fluorine source to obtain binary copolymerized perfluoropolyether, wherein the active fluorine source is obtained by irradiating a fluoridation reagent by ultraviolet light, and the fluoridation reagent is fluorine gas, nitrogen trifluoride or mixed gas of carbonyl fluoride and inert gas.
3. The method of claim 2, wherein the reaction time in step (1) is 11.5 to 12.5 hours.
4. The method of claim 2, wherein the step (2) is a stabilization treatment for 5 to 30 hours.
5. The method of claim 2, further comprising fractionally separating the resulting binary copolymerized perfluoropolyether by molecular distillation to obtain the binary copolymerized perfluoropolyether having different average molecular weights.
6. The method of preparing as claimed in claim 2, wherein the method of preparing the initiator comprises the steps of:
in the atmosphere of fluorine, perfluoro carboxyl glycol diester or N, N-bis (perfluoroalkyl acyloxyalkyl) amine reacts with metal fluoride at a low temperature range of minus 30 ℃ to minus 10 ℃, and then reacts in 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 polar aprotic solvent at a high temperature range of 50 ℃ to 80 ℃ to obtain perfluoro glycol metal salt or perfluoro glycol amine metal salt with different concentrations; the metal fluoride is selected from potassium fluoride, cesium fluoride, rubidium fluoride or silver fluoride.
7. The preparation method according to claim 6, wherein the reaction time in the low temperature range is 10 to 15 hours; the reaction time in the high temperature interval is 8-15 h.
8. The method for preparing the binary copolymerized perfluoropolyether according to claim 6, wherein the perfluorocarboxylic glycol diester is selected from the group consisting of diethylene glycol pentafluorobropionate, triethylene glycol trifluoroacetate or tetraethylene glycol trifluoroacetate; the N, N-bis (perfluoroalkyl acyloxyalkyl) amine is selected from N, N-bis (pentafluoropropionyloxyethyl) amine, N-bis (pentafluoropropionyloxypropyl) amine, N-bis (trifluoroacetoxyethyl) amine or N, N-bis (trifluoroacetoxybutyl) amine; the metal fluoride is cesium fluoride; the reaction solvent is tetraethylene glycol dimethyl ether or tetraethylene glycol diethyl ether.
9. The process according to claim 2, wherein the molar amount of initiator to total molar amount of monomers is 1: 30-750.
10. The process of claim 2 wherein the viscosity modifier of step (1) is hexafluoropropylene; the molar amount of the viscosity modifier is 0.3 to 3.0 times the total molar amount of the monomers.
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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 |
| CN104892919A (en) * | 2014-03-04 | 2015-09-09 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for polyhexafluoroepoxypropanediacyl fluoride |
| 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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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 |
| CN104892919A (en) * | 2014-03-04 | 2015-09-09 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for polyhexafluoroepoxypropanediacyl fluoride |
| 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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