CN105111351A - Method for preparing special fluoroether surfactant - Google Patents
Method for preparing special fluoroether surfactant Download PDFInfo
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Abstract
The invention discloses a method for preparing a special fluoroether surfactant. The method comprises the steps of adding deionized water and a fluoroether oligomer, of which the average molecular weight is 300-1,500, into a hydrolysis reaction kettle according to the weight ratio of about (1: 15) to (3: 1), carrying out stirring heating, maintaining the internal temperature of the kettle to be about 30-200 DEG C, hydrolyzing unstable terminal groups of the fluoroether oligomer into carboxylic acid terminal groups, carrying out reaction for half an hour to 8 hours, then, standing a reaction solution to carry out layering, removing an upper-layer aqueous solution through sucking, adding an approximately equal volume of clean deionized water into the hydrolysis kettle so as to clean reactants, carrying out stirring for about half an hour at normal temperature, then, removing an upper-layer aqueous solution through sucking, repeating the cleaning method for 1-3 times, and discharging the reactant, thereby preparing the fluoroether surfactant containing the carboxylic acid terminal groups.
Description
Technical field
The present invention relates to a kind of preparation method of extraordinary fluorine ether surface active agent, particularly relate to extraordinary fluorine ether oligomer and derivative fluorine ether surface active agent preparation method thereof.
Background technology
Fluorine ether oil, the especially oligopolymer of fluorine ethers have excellent physical surface performance and lower temperature resistance, and chemical stability, all has a wide range of applications in each fields such as chemical materials, mechanical seal, high temperature resistant lubrication, space flight military project, novel materials.Fluorochemical monomer and oxygen are adopted illumination or irradiation at sub-zero temperature, again through end group process, the fluorine material with outstanding surface property can be obtained, due to its property, this material becomes a kind of functional fluoropolymer material of high-end applications, such as, for auxiliary chemicals, additive, tensio-active agent, makeup, protective coating, garment material, sealing material, high temperature resistant luboil, washing agent for electronic materials etc.
Fluorine ether oligomer material is because having excellent high and low temperature resistance, mechanical property, and surfactivity and chemical stability, be just used to manufacture high temperature-resistant grease, sealing material, tensio-active agent, coating and garment material etc. since the eighties.Fluorine ether oligomer usually adopts tetrafluoroethylene, R 1216 monomer in industry preparation, with oxygen, carries out oxypolymerization prepare fluorine ether oligomer by low temperature ultra-violet lamp photograph or irradiance method.But compared with the Perfluorocaprylic Acid that the surfactivity of this kind of fluorine ether oligomer liquid and general fluoropolymer letex polymerization are conventional, stability of emulsion is poor, but cause problem of environmental pollution due to Perfluorocaprylic Acid, be badly in need of finding Perfluorocaprylic Acid substitute.In addition the surperficial oil preventing performance of this kind of fluorine ether oligomer does not have three traditional anti-fluoropolymers good, and its surface tension performance still needs to improve.In addition, the resistance to low temperature of Conventional fluoroelastomeric is bad, and for inclined viton, its lower temperature resistance is generally minimum to subzero 30 degree of just easy embrittlement, and this is inadequate to exploitation aviation and wide, needs to improve again.
Summary of the invention
The invention provides a kind of preparation method of extraordinary fluorine ether surface active agent, it can improve the surfactivity of fluorine ether oligomer, and its application, except as Perfluorocaprylic Acid substitute, also can be made fluorine ether oil, and the critical materials etc. of low temperature resistant viton.
Present invention employs following technical scheme: a kind of preparation method of extraordinary fluorine ether surface active agent, it obtains by the following method: add in hydrolytic reaction pot deionized water and molecular-weight average 300 ~ 1500 fluorine ether oligomer, weight ratio is about 1:15 ~ 3:1, and stir intensification, temperature in the kettle is maintained until about 30 ~ 200 DEG C, the unstable end-group of fluorine ether oligomer can be hydrolyzed into carboxylic end group, reaction times was about half an hour by 8 hours, layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about equivalent in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described purging method 1 ~ 3 time, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group.
Described hydrolysis reaction temperature in the kettle preferably maintains 50 ~ 200 DEG C, and unstable end-group is acyl fluorine – COF and acyl chlorine – COCl.Described fluorine ether oligomer obtains by the following method: first by fluorochemical monomer A, B is with the ratio of More than 99:1 ~ 65:35, pass into the photochemical low-temp reaction still dehumidified, wherein fluorochemical monomer A: containing the tetrafluoroethylene of R 1216 0 ~ 90% More ratio of 10 ~ 100% More's ratios, fluorochemical monomer B: containing hexafluoropropylene-based alkyl oxide CF2=CFCF2-O-Rf, Rf is CnF2n+1, n=1 ~ 5: the jacket temperature of reactor will maintain below the boiling point of fluorine-containing mix monomer in advance, fluorochemical monomer is entered in still and can maintain liquid phase, general at subzero 70 degree ~ 0 degree, then stirring is opened, open ultraviolet lamp, pass in the oxygen and optional molecular weight regulator to fluorochemical monomer liquid phase dehumidified and start photochemical oxidative polymerization, the wherein purity at least 95% of oxygen, the oxygen total amount entered in photochmeical reaction still is at least 1.5 times of the total More's number of fluorochemical monomer, molecular weight regulator is fluorine-containing chloride, fluorine-containing brominated, or it is fluorine-containing containing iodine organification compound, containing 1 ~ 3 carbon, optionally there is trifluorochloromethane CF3-Cl, methyl chlorofluoride CF2Cl2, bromotrifluoromethane CF3-Br, CF3I CF3-I, trifluorochloroethylene, dichlorodifluoroethylene, the molecular weight regulator total amount entered in this photochmeical reaction still is at least 0 ~ 50% of the total More's number of fluorochemical monomer, molecular weight regulator consumption is larger, molecular weight of product is lower, photochmeical reaction is with ultraviolet catalytic, oxygen is allowed to become the Sauerstoffatom (O-) of band free radical, go to start radical polymerization, liquid phase fluorochemical monomer and the copolymerization of gas phase Sauerstoffatom, this is gas liquid reaction, gas phase oxygen demand and liquid phase fluorochemical monomer fully stir, could fully react, molecular weight regulator plays the effect of Raolical polymerizable end-blocking, reaction times half an hour by 24 hours between, fluorochemical monomer changes into the yield about 5 ~ 50% of fluorine ether oligomer, preferred yield about 10 ~ 30%, the composition of reactant is very complicated, it not single product, molecular weight distribution is 200 ~ 20000, be generically and collectively referred to as fluorine ether oligomer, its viscosity is about 1 ~ 500cPs at 25 degree of temperature, the chemical structure of described product is very complicated, because raw material composition is different, can (– CF2O-be contained) the different permutation and combination of the segment such as (-CF2CF2O-) (-CF2CF (CF3) O-) (-CF2CF (CF2OCF3) O-) (-CF2CF (CF2OC2F5) O-) (-CF2CF (CF2OC3F7) O-), its terminal group can contain-CF3,-CF2Cl,-CF2Br,-CF2I,-COF,-COCl,-COBr,-COI, fluorochemical monomer A, B is preferably 95:5 ~ 80:20 with More's ratio, hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3 is preferably had containing hexafluoropropylene-based alkyl oxide, perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7 or its mixture, fluorochemical monomer enters in still can maintain liquid phase preferably at subzero 60 degree ~ subzero 30 degree, the oxygen total amount entered in photochmeical reaction still is greater than the total More's number of fluorochemical monomer 2 times, the molecular weight regulator total amount entered in this photochmeical reaction still is preferably 1 ~ 30% of the total More's number of fluorochemical monomer.The molecular-weight average of described fluorine ether oligomer is 300 ~ 1500, its viscosity is about 1 ~ 20cPs at 25 degree of temperature, be applicable to doing fluorine ether surface active agent, Perfluorocaprylic Acid substitute can be become, the molecular-weight average of described fluorine ether oligomer is more than 1500, its viscosity is about 20 ~ 500cPs at 25 degree of temperature, also be applicable to the important application doing fluorine ether oil and high temperature resistant luboil fat thereof, above product or its mixture also can as the polymerization technique of extraordinary viton auxiliary agents used, especially low temperature resistant viton, more than classification can be separated obtained fluorine ether oligomer crude product and use according to its boiling range difference with rectificating method.Described fluorine ether surface active agent, its acid number is between 60 to 120, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid, when this kind of fluorine ether surface active agent uses in aqueous solution, can in synthesize amine salt or an alkali metal salt, an alkali metal salt is sodium salt or sylvite.
Described its acid number of fluorine ether surface active agent is preferably between 70 to 100.Described fluorine ether oil is obtained by following operation: the fluorine ether oligomer of molecular-weight average more than 1500 is not hydrolyzed crude product in photochmeical reaction still, carries out high temperature coupled reaction, photochmeical reaction at high temperature removes peroxide bridge and the unstable end-group of fluorine ether oligomer, such as peroxide bridge Rf-O-O-Rf is changed into Rf-O-Rf, unstable end-group as acyl fluorides-COF, acyl chlorides-COCl etc. is interrupted, cause the free radical of Rf-, the free radical of two Rf-coupling can become stable fluorinated ether chain and connects, high temperature refers between 50 to 200 degree, reaction times be about half an hour ~ 12 hours, fluorine ether oil crude product after the coupling of described preparation carries out fluoridizing (F2), reaction conditions is under oxygen condition with reactor, fluorine ether oil crude product after described coupling is passed into fluorine gas, it is kind of a gas liquid reaction, stir very crucial, also its end group of Useful UV photochemical catalysis fracture during reaction, make end group can thoroughly be fluorinated into comparatively stable end groups as-CF3, temperature of reaction is at 50 to 200 degree, reaction pressure is at 1 to 20 normal atmosphere, reaction times was about half an hour by 24 hours.Described extraordinary viton is obtained by following operation: in withstand voltage reactor, add deionized water, and fluorine ether carboxylate is tensio-active agent, and after reactor deoxygenation, heated and stirred, passes into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, and preferred concentration is 0.05% ~ 2.0%, and radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide.The low temperature resistant viton of described special type is obtained by following operation: in withstand voltage reactor, add deionized water and fluorine ether carboxylate is tensio-active agent and fluorine ether oil, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, preferred concentration is 0.05% ~ 2.0%, the molecular weight of described fluorine ether oil is 1500 ~ 20000, the concentration of described fluorine ether oil in final emulsion product is 0.01% ~ 3%, preferred concentration is 1% ~ 3%, described radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide, described low temperature resistant viton is in 40 degrees below zero not embrittlement.
The present invention has following beneficial effect: the present invention's photochmeical reaction used and extraordinary fluorine monomer, the fluorine ether oligomer obtained has many unexpected, of great value application, low-molecular-weight fluorine ether oligomer can after hydrolysis, make fluorine ether carboxylic acid, its surface tension, lower than Perfluorocaprylic Acid, can be tested and prove that alternative Perfluorocaprylic Acid does fluoro containing polymers Dispersing Emulsion Polymerization.This extraordinary fluorine ether oligomer also can be made into thermostable fluorine ether oil, invent described fluorine ether carboxylic acid and fluorine ether oil with this to arrange in pairs or groups together and prepare viton, experiment proves good than alone Perfluorocaprylic Acid of its resistance to low temperature of viton of gained, can obtain needed for the sealing material markets such as space flight and aviation, automobile, semi-conductor industry: the low temperature viton of ability 40 degrees below zero, this extraordinary low temperature resistant viton more can be accepted by market.The invention discloses a kind of extraordinary fluorine ether oligomer, is use special fluorochemical monomer mixture to carry out photochemical oxidative polymerization gained.The fluorine ether oligomer obtained has many unexpected, of great value application.Its molecular-weight average is 300 ~ 1500, and its viscosity is about 1 ~ 20cPs at 25 degree of temperature, acid number does fluorine ether surface active agent in the applicable processing of 70 ~ 100, can become Perfluorocaprylic Acid substitute.The molecular-weight average of described fluorine ether oligomer is more than 1500, and its viscosity is about 20 ~ 500cPs at 25 degree of temperature, be also applicable to the important application that fluorine ether oil and high temperature resistant luboil fat etc. thereof are done in processing.Above product or its mixture also can as the polymerization technique of extraordinary viton auxiliary agents used, and especially prepare low temperature resistant viton, its resistance to low temperature can reach 40 degrees below zero, more can by space flight and aviation, automotive industry market accept.
Embodiment
The invention provides a kind of preparation method of extraordinary fluorine ether surface active agent, it is characterized in that it obtains by the following method: add in hydrolytic reaction pot deionized water and molecular-weight average 300 ~ 1500 fluorine ether oligomer, weight ratio is about 1:15 ~ 3:1, and stir intensification, temperature in the kettle is maintained until about 30 ~ 200 DEG C, the unstable end-group of fluorine ether oligomer can be hydrolyzed into carboxylic end group, reaction times was about half an hour by 8 hours, layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about equivalent in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described purging method 1 ~ 3 time, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group, described hydrolysis reaction temperature in the kettle preferably maintains 50 ~ 200 DEG C, unstable end-group is Xian Fu – COF and Xian Lv – COCl, described fluorine ether oligomer obtains by the following method: first by fluorochemical monomer A, B is with the ratio of More than 99:1 ~ 65:35, pass into the photochemical low-temp reaction still dehumidified, wherein fluorochemical monomer A: containing the tetrafluoroethylene of R 1216 0 ~ 90% More ratio of 10 ~ 100% More's ratios, fluorochemical monomer B: containing hexafluoropropylene-based alkyl oxide CF2=CFCF2-O-Rf, Rf is CnF2n+1, n=1 ~ 5: the jacket temperature of reactor will maintain below the boiling point of fluorine-containing mix monomer in advance, fluorochemical monomer is entered in still and can maintain liquid phase, general at subzero 70 degree ~ 0 degree, then stirring is opened, open ultraviolet lamp, pass in the oxygen and optional molecular weight regulator to fluorochemical monomer liquid phase dehumidified and start photochemical oxidative polymerization, the wherein purity at least 95% of oxygen, the oxygen total amount entered in photochmeical reaction still is at least 1.5 times of the total More's number of fluorochemical monomer, molecular weight regulator is fluorine-containing chloride, fluorine-containing brominated, or it is fluorine-containing containing iodine organification compound, containing 1 ~ 3 carbon, optionally there is trifluorochloromethane CF3-Cl, methyl chlorofluoride CF2Cl2, bromotrifluoromethane CF3-Br, CF3I CF3-I, trifluorochloroethylene, dichlorodifluoroethylene, the molecular weight regulator total amount entered in this photochmeical reaction still is at least 0 ~ 50% of the total More's number of fluorochemical monomer, molecular weight regulator consumption is larger, molecular weight of product is lower, photochmeical reaction is with ultraviolet catalytic, oxygen is allowed to become the Sauerstoffatom (O-) of band free radical, go to start radical polymerization, liquid phase fluorochemical monomer and the copolymerization of gas phase Sauerstoffatom, this is gas liquid reaction, gas phase oxygen demand and liquid phase fluorochemical monomer fully stir, could fully react, molecular weight regulator plays the effect of Raolical polymerizable end-blocking, reaction times half an hour by 24 hours between, fluorochemical monomer changes into the yield about 5 ~ 50% of fluorine ether oligomer, preferred yield about 10 ~ 30%, the composition of reactant is very complicated, it not single product, molecular weight distribution is 200 ~ 20000, be generically and collectively referred to as fluorine ether oligomer, its viscosity is about 1 ~ 500cPs at 25 degree of temperature, the chemical structure of described product is very complicated, because raw material composition is different, can (– CF2O-be contained) the different permutation and combination of the segment such as (-CF2CF2O-) (-CF2CF (CF3) O-) (-CF2CF (CF2OCF3) O-) (-CF2CF (CF2OC2F5) O-) (-CF2CF (CF2OC3F7) O-), its terminal group can contain-CF3,-CF2Cl,-CF2Br,-CF2I,-COF,-COCl,-COBr,-COI, fluorochemical monomer A, B is preferably 95:5 ~ 80:20 with More's ratio, hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3 is preferably had containing hexafluoropropylene-based alkyl oxide, perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7 or its mixture, fluorochemical monomer enters in still can maintain liquid phase preferably at subzero 60 degree ~ subzero 30 degree, the oxygen total amount entered in photochmeical reaction still is greater than the total More's number of fluorochemical monomer 2 times, the molecular weight regulator total amount entered in this photochmeical reaction still is preferably 1 ~ 30% of the total More's number of fluorochemical monomer, the molecular-weight average of described fluorine ether oligomer is 300 ~ 1500, its viscosity is about 1 ~ 20cPs at 25 degree of temperature, be applicable to doing fluorine ether surface active agent, Perfluorocaprylic Acid substitute can be become, the molecular-weight average of described fluorine ether oligomer is more than 1500, its viscosity is about 20 ~ 500cPs at 25 degree of temperature, also be applicable to the important application doing fluorine ether oil and high temperature resistant luboil fat thereof, above product or its mixture also can as the polymerization technique of extraordinary viton auxiliary agents used, especially low temperature resistant viton, more than classification can be separated obtained fluorine ether oligomer crude product and use according to its boiling range difference with rectificating method, described fluorine ether surface active agent, its acid number is between 60 to 120, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid, when this kind of fluorine ether surface active agent uses in aqueous solution, can in synthesize amine salt or an alkali metal salt, an alkali metal salt is sodium salt or sylvite, described its acid number of fluorine ether surface active agent is preferably between 70 to 100, described fluorine ether oil is obtained by following operation: the fluorine ether oligomer of molecular-weight average more than 1500 is not hydrolyzed crude product in photochmeical reaction still, carries out high temperature coupled reaction, photochmeical reaction at high temperature removes peroxide bridge and the unstable end-group of fluorine ether oligomer, such as peroxide bridge Rf-O-O-Rf is changed into Rf-O-Rf, unstable end-group as acyl fluorides-COF, acyl chlorides-COCl etc. is interrupted, cause the free radical of Rf-, the free radical of two Rf-coupling can become stable fluorinated ether chain and connects, high temperature refers between 50 to 200 degree, reaction times be about half an hour ~ 12 hours, fluorine ether oil crude product after the coupling of described preparation carries out fluoridizing (F2), reaction conditions is under oxygen condition with reactor, fluorine ether oil crude product after described coupling is passed into fluorine gas, it is kind of a gas liquid reaction, stir very crucial, also its end group of Useful UV photochemical catalysis fracture during reaction, make end group can thoroughly be fluorinated into comparatively stable end groups as-CF3, temperature of reaction is at 50 to 200 degree, reaction pressure is at 1 to 20 normal atmosphere, reaction times was about half an hour by 24 hours, described extraordinary viton is obtained by following operation: in withstand voltage reactor, add deionized water, fluorine ether carboxylate is tensio-active agent, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, preferred concentration is 0.05% ~ 2.0%, radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide, the low temperature resistant viton of described special type is obtained by following operation: in withstand voltage reactor, add deionized water and fluorine ether carboxylate is tensio-active agent and fluorine ether oil, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, preferred concentration is 0.05% ~ 2.0%, the molecular weight of described fluorine ether oil is 1500 ~ 20000, the concentration of described fluorine ether oil in final emulsion product is 0.01% ~ 3%, preferred concentration is 1% ~ 3%, described radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide, described low temperature resistant viton is in 40 degrees below zero not embrittlement.
First the present invention provides a kind of preparation method of extraordinary fluorine ether oligomer, described preparation method comprises first by fluorochemical monomer A, B is with the ratio of More's ratio (99:1) ~ (65:35), preferred with the ratio of More's ratio (95:5) ~ (80:20), pass into the photochemical low-temp reaction still dehumidified, wherein fluorochemical monomer A: containing the R 1216 of (10 ~ 100% Mores' ratio) and the tetrafluoroethylene of (0 ~ 90% More's ratio); Fluorochemical monomer B: containing hexafluoropropylene-based alkyl oxide CF2=CFCF2-O-Rf, Rf is CnF2n+1, n=1 ~ 5: wherein preferably have hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3, perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7, or its mixture; The jacket temperature of reactor will maintain below the boiling point of fluorine-containing mix monomer in advance, fluorochemical monomer is entered in still and can maintain liquid phase, generally at subzero 70 degree ~ 0 degree, preferably at subzero 60 degree ~ subzero 30 degree; Then stirring is opened, open ultraviolet lamp, pass in the oxygen and optional molecular weight regulator to fluorochemical monomer liquid phase dehumidified and start photochemical oxidative polymerization, the wherein purity at least 95% of oxygen, the oxygen total amount entered in photochmeical reaction still is at least 1.5 times of the total More's number of fluorochemical monomer, is preferably greater than 2 times; Molecular weight regulator is fluorine-containing chloride, fluorine-containing brominated or fluorine-containing containing iodine organification compound (containing 1 ~ 3 carbon), optionally has trifluorochloromethane CF3-Cl, methyl chlorofluoride CF2Cl2, bromotrifluoromethane CF3-Br, CF3I CF3-I, trifluorochloroethylene, dichlorodifluoroethylene etc.The molecular weight regulator total amount entered in this photochmeical reaction still is at least 0 ~ 50%, preferred 1 ~ 30% of the total More's number of fluorochemical monomer, and molecular weight regulator consumption is larger, and molecular weight of product is lower.Photochmeical reaction is with ultraviolet catalytic, oxygen is allowed to become the Sauerstoffatom (O-) of band free radical, go to start radical polymerization, liquid phase fluorochemical monomer and the copolymerization of gas phase Sauerstoffatom, this is gas liquid reaction, gas phase oxygen demand and liquid phase fluorochemical monomer fully stir, and could fully react, and molecular weight regulator plays the effect of Raolical polymerizable end-blocking.Reaction times half an hour by 24 hours between.Fluorochemical monomer changes into the yield about 5 ~ 50% of fluorine ether oligomer, preferred yield about 10 ~ 30%.The composition of reactant is very complicated, is not single product, and molecular weight distribution, 200 ~ 20000, is generically and collectively referred to as fluorine ether oligomer.Its viscosity is about 1 ~ 500cPs at 25 degree of temperature.The chemical structure of product is very complicated, because raw material composition is different, can (– CF2O-be contained) the different permutation and combination of the segment such as (-CF2CF2O-) (-CF2CF (CF3) O-) (-CF2CF (CF2OCF3) O-) (-CF2CF (CF2OC2F5) O-) (-CF2CF (CF2OC3F7) O-), its terminal group can contain-CF3 ,-CF2Cl,-CF2Br,-CF2I ,-COF ,-COCl,-COBr ,-COI etc.
Wherein, the molecular-weight average of described fluorine ether oligomer is 300 ~ 1500, and its viscosity is about 1 ~ 20cPs at 25 degree of temperature, is applicable to doing fluorine ether surface active agent, can become Perfluorocaprylic Acid substitute.The molecular-weight average of described fluorine ether oligomer is more than 1500, and its viscosity is about 20 ~ 500cPs at 25 degree of temperature, is also applicable to the important application doing fluorine ether oil and high temperature resistant luboil fat etc. thereof.Above product or its mixture also can as the polymerization technique of extraordinary viton auxiliary agents used, especially low temperature resistant viton.More than classification can be separated obtained fluorine ether oligomer crude product and use according to its boiling range difference with rectificating method.
Alternatively, the preparation method of described fluorine ether surface active agent comprises: add in hydrolytic reaction pot deionized water and molecular-weight average 300 ~ 1500 fluorine ether oligomer, weight ratio is about (1:15) ~ and (3:1), and stir intensification, temperature in the kettle is maintained until about 30 ~ 200 DEG C, and the unstable end-group (as acyl fluorides-COF, acyl chlorides-COCl etc.) of fluorine ether oligomer can be hydrolyzed into carboxylic end group, reaction times was about half an hour by 8 hours, and preferred temperature in the kettle maintains 50 ~ 200 DEG C, layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about equivalent in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described purging method 1 ~ 3 time, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group, its acid number is between 60 to 120, preferred between 80 to 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid.When this kind of fluorine ether surface active agent uses in aqueous solution, synthesize amine salt or an alkali metal salt in suggestion, as sodium salt or sylvite etc.
Alternatively, the preparation method 1 of described fluorine ether oil is as follows: the fluorine ether oligomer of molecular-weight average more than 1500 is not hydrolyzed crude product in photochmeical reaction still, carries out high temperature coupled reaction, photochmeical reaction at high temperature removes peroxide bridge and the unstable end-group of fluorine ether oligomer, such as, peroxide bridge Rf-O-O-Rf is changed into Rf-O-Rf.Unstable end-group as acyl fluorides-COF, acyl chlorides-COCl etc. is interrupted, and causes the free radical of Rf-, and the free radical of two Rf-coupling can become stable fluorinated ether chain and connect.High temperature refer to 50 to 200 degree between, the reaction times be about half an hour ~ 12 hours.
Preferably, the preparation method 2 of described fluorine ether oil is as follows: carried out fluoridizing (F2) by the crude product obtained by the preparation method 1 of described fluorine ether oil.Reaction conditions is under oxygen condition with reactor, crude product obtained by the preparation method 1 of described fluorine ether oil is passed into fluorine gas, is kind of a gas liquid reaction, stirs very crucial, during reaction also its end group of Useful UV photochemical catalysis fracture, make end group can thoroughly be fluorinated into comparatively stable end groups as-CF3 etc.Temperature of reaction is at 50 to 200 degree, and reaction pressure is at 1 to 20 normal atmosphere, and the reaction times was about half an hour by 24 hours.
Alternatively, the polymerization technique of described extraordinary viton is as follows: in withstand voltage reactor, add deionized water and fluorine ether carboxylate described above is tensio-active agent, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More's ratio (20% ~ 70%), (10% ~ 40%) R 1216, the tetrafluoroethylene of (0% ~ 70%), all the other optional comonomers (0% ~ 40%) are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere.
Preferably, the average acid number of described fluorine ether carboxylic acid surfactant 60 ~ 120, preferred average acid number 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m),
Optionally, the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, and preferred concentration is 0.05% ~ 2.0%.
Optionally, radical initiator be selected from persulphate, hydrogen peroxide or organo-peroxide any one or its combination.
The present invention also provides a kind of extraordinary low temperature resistant viton (not embrittlement under 40 degrees below zero environment) and preparation method thereof, described manufacture method comprises following operation: in withstand voltage reactor, add deionized water and fluorine ether carboxylate described above is tensio-active agent and fluorine ether oil described above, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More's ratio (20% ~ 70%), (10% ~ 40%) R 1216, the tetrafluoroethylene of (0% ~ 70%), all the other optional comonomers (0% ~ 40%) are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere.
Optionally, the average acid number of described fluorine ether carboxylic acid surfactant 60 ~ 120, preferred average acid number 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m),
Optionally, the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, and preferred concentration is 0.05% ~ 2.0%.
Optionally, the molecular weight of described fluorine ether oil is 1500 ~ 20000, and the concentration of described fluorine ether oil in final emulsion product is 0.01% ~ 3%, and preferred concentration is 1% ~ 3%.
Optionally, described radical initiator be selected from persulphate, hydrogen peroxide or organo-peroxide any one or its combination.
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.
For making the object, technical solutions and advantages of the present invention clearly understand, below in conjunction with specific embodiment, the present invention is described in more detail.
The preparation of embodiment 1(lower molecular weight 300 ~ 1500 fluorine ether oligomer)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(90% R 1216 of 9.9 kilograms, 10% tetrafluoroethylene), the fluorochemical monomer B of 0.1 kilogram: hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 3.5 liters/min) at the bottom of still, also pass into methyl chlorofluoride (about 0.45 liter/min) simultaneously, temperature in the kettle controls at subzero 35 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtain the fluorine ether oligomer transparent liquid of the molecular weight about 300 ~ 1500 of about 1.97 kilograms, density is about 1.69 grams per milliliters.
The preparation of embodiment 2(lower molecular weight 300 ~ 1500 fluorine ether oligomer)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(80% R 1216 of 9.5 kilograms, 20% tetrafluoroethylene), the fluorochemical monomer B of 0.5 kilogram: hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 3.6 liters/min) at the bottom of still, also pass into trifluorobromomethane (about 0.41 liter/min) simultaneously, temperature in the kettle controls at subzero 35 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtain the fluorine ether oligomer transparent liquid of the molecular weight about 300 ~ 1500 of about 1.69 kilograms, density is about 1.66 grams per milliliters.
The preparation of embodiment 3(lower molecular weight 300 ~ 1500 fluorine ether oligomer)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(99% R 1216 of 8.0 kilograms, 1% tetrafluoroethylene), the fluorochemical monomer B of 2.0 kilograms: perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 3.9 liters/min) at the bottom of still, also pass into Freon 13 (about 0.43 liter/min) simultaneously, temperature in the kettle controls at subzero 30 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtain the fluorine ether oligomer transparent liquid of the molecular weight about 300 ~ 1500 of about 2.09 kilograms, density is about 1.68 grams per milliliters.
The preparation of embodiment 4(high molecular >1500 fluorine ether oligomer)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(80% R 1216 of 9.5 kilograms, 20% tetrafluoroethylene), the fluorochemical monomer B of 0.5 kilogram: hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 3.8 liters/min) at the bottom of still, do not add any molecular weight regulator, temperature in the kettle controls at subzero 35 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, the molecular-weight average obtaining about 2.68 kilograms is about the fluorine ether oligomer transparent liquid of >1000, density is about 1.67 grams per milliliters.
The preparation of embodiment 5(high molecular >1500 fluorine ether oligomer)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(99% R 1216 of 6.5 kilograms, 1% tetrafluoroethylene), the fluorochemical monomer B of 3.5 kilograms: perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 4.2 liters/min) at the bottom of still, do not add any molecular weight regulator, temperature in the kettle controls at subzero 35 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, the molecular-weight average obtaining about 2.89 kilograms is about the fluorine ether oligomer transparent liquid of >1500, density is about 1.68 grams per milliliters.
Prepared by embodiment 6(fluorine ether surface active agent)
The molecular weight adding 1 kilogram of deionized water and 1.8 kilograms in 5 premium on currency solution reaction kettles 300 ~ 1500 fluorine ether oligomer (obtained from embodiment 1), and stir intensification, temperature in the kettle is maintained until about 180 DEG C, the unstable end-group of fluorine ether oligomer is (as acyl fluorides-COF, acyl chlorides-COCl etc.) be hydrolyzed into carboxylic end group, in about 3 hours reaction times, temperature in the kettle maintains 150 ~ 190 DEG C; Layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about 1 kilogram in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described cleaning side 3 times, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group, its acid number is 81, its surface tension in water 0.1% concentration be about ~ 18 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid.
Prepared by embodiment 7(fluorine ether surface active agent)
The molecular weight adding 1 kilogram of deionized water and 1.5 kilograms in 5 premium on currency solution reaction kettles 300 ~ 1500 fluorine ether oligomer (obtained from embodiment 2), and stir intensification, temperature in the kettle is maintained until about 170 DEG C, the unstable end-group (as acyl fluorides-COF Xian Xiu – COBr etc.) of fluorine ether oligomer is hydrolyzed into carboxylic end group, in about 2 hours reaction times, temperature in the kettle maintains 130 ~ 180 DEG C; Layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about 1 kilogram in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described cleaning side 3 times, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group, its acid number is 98, its surface tension in water 0.1% concentration be about ~ 16 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid.
Prepared by embodiment 8(fluorine ether surface active agent)
The molecular weight adding 1 kilogram of deionized water and 1.9 kilograms in 5 premium on currency solution reaction kettles 300 ~ 1500 fluorine ether oligomer (obtained from embodiment 3), and stir intensification, temperature in the kettle is maintained until about 130 DEG C, the unstable end-group of fluorine ether oligomer is (as acyl fluorides-COF, acyl chlorides-COCl etc.) be hydrolyzed into carboxylic end group, in about 4 hours reaction times, temperature in the kettle maintains 100 ~ 150 DEG C; Layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about 1 kilogram in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described cleaning side 3 times, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group, its acid number is 66, its surface tension in water 0.1% concentration be about ~ 13 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid.
Embodiment 9(fluorine ether oil preparation-coupled reaction)
In the coupled reaction still of 5 liters, the fluorine ether oligomer of the molecular-weight average of 2 kilograms more than 1500 is not hydrolyzed crude product (from embodiment 4) in still, carries out high temperature coupled reaction, coupled reaction is by kind of a photochmeical reaction, peroxide bridge and the unstable end-group of fluorine ether oligomer is at high temperature removed by UV-light, peroxide bridge Rf-O-O-Rf is changed into Rf-O-Rf, also unstable end-group as acyl fluorides-COF etc. interrupts by ultraviolet luminous energy, cause the free radical of Rf-, the free radical of two Rf-coupling can become stable fluorinated ether chain and connects.Couple temperature controls between 100 to 150 degree.In about 6 hours reaction times, after photochemical coupling, there is fluoro phosgene by product to occur, being gathered into waste water with closing in buck.Obtain the fluorine ether oil that the coupling of about 1.89 kilograms is good.
Embodiment 10(fluorine ether oil preparation-fluoridation)
In the fluoridation still of 5 liters, the fluorine ether oligomer of the molecular-weight average of 2 kilograms more than 1500 is not hydrolyzed crude product (from embodiment 5) in still, carries out fluorine element (F2) fluoridation, reaction conditions is after first using nitrogen deoxygenation with fluoridation still, the mixed gas passing into delivery of fluorine/nitrogen (20:80 More ratio) enters fluorine ether crude product, it is kind of a gas liquid reaction, open stirring, gas-liquid agitation of make suring reaction is sufficient, make end group can thoroughly be fluorinated into comparatively stable end groups as-CF3 etc.Temperature of reaction control 90 to 120 degree, reaction pressure at 6 ~ 7 normal atmosphere, about 12 hours reaction times.There is fluoro phosgene by product to occur, close in all tail gas bucks and be gathered into wastewater treatment.Obtain the fluorine ether oil of the end group stabilization of about 1.87 kilograms.
The manufacture of embodiment 11(viton emulsion: not containing Perfluorocaprylic Acid, fluorine-containing ether carboxylic acid)
In the autoclave of about 20 liters, the fluorine ether carboxylic acid ammonium of the deionized water and 90g that first add 10L is (from embodiment 6, acid number about 81), vacuumizing deoxygenation (until oxygen level <20ppm) in still, open stirring, temperature in the kettle is raised to about 70 DEG C, and in still, then pass into the mixed gas (60:30:10 More ratio) of vinylidene and R 1216 and perfluoro methyl vinyl ether, still internal pressure reaches about 25 kilograms.5 grams of ammonium persulphates (being dissolved in advance in 500 ml waters) are added as initiator in still, started copolymer reacts, temperature in the kettle maintains 80 ~ 100 DEG C, still internal pressure is made to maintain about 25 kilograms by mixed gas in reaction process, sustained reaction reaches about 33% to emulsion solid content, after temperature in the kettle is down to room temperature, stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtains and stablizes viton emulsion, prove that the alternative Perfluorocaprylic Acid of fluorine ether carboxylic acid does polyreaction, the median size of its primary particle is about 120nm.Get sample emulsion through breakdown of emulsion, cohesion, after drying, detect this viton without fusing point, density is about 1.79g/cm
3.The embrittlement temperature of the low temperature flexibility of viton is about subzero 33 degree.
Prepared by embodiment 12(low temperature viton: not containing Perfluorocaprylic Acid, fluorine-containing ether carboxylic acid and fluorine ether oil)
In the autoclave of about 20 liters, the fluorine ether carboxylic acid ammonium of the deionized water and 90g that first add 10L is (from embodiment 7, acid number about 98) and the fluorine ether oil (from embodiment 9) of 160 grams, vacuumizing deoxygenation (until oxygen level <20ppm) in still, open high-speed stirring pre-emulsification fluorine ether oil, temperature in the kettle is raised to about 70 DEG C, then in still, pass into the mixed gas (50:30:20 More ratio) of vinylidene and R 1216 and perfluoro propyl vinyl ether, still internal pressure reaches about 25 kilograms.5 grams of ammonium persulphates (being dissolved in advance in 500 ml waters) are added as initiator in still, started copolymer reacts, temperature in the kettle maintains 80 ~ 100 DEG C, still internal pressure is made to maintain about 25 kilograms by mixed gas in reaction process, sustained reaction reaches about 29% to emulsion solid content, after temperature in the kettle is down to room temperature, stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtains and stablizes viton emulsion, prove that the alternative Perfluorocaprylic Acid of fluorine ether carboxylic acid does polyreaction, the median size of its primary particle is about 90nm.Get sample emulsion through breakdown of emulsion, cohesion, after drying, detect this viton without fusing point, density is about 1.88g/cm
3.The embrittlement temperature of the low temperature flexibility of this viton is about subzero 46 degree.
Prepared by comparative example 1(lower molecular weight 300 ~ 1500 fluorine ether oligomer, not fluoridize monomers B)
In the photochmeical reaction still of about 10 liters of internal volumes, first nitrogen deoxygenation and dehumidifying is used, jacket temperature is reduced to subzero 70 degree, then in still, pass into the fluorochemical monomer A(70% R 1216 of 10 kilograms, 30% tetrafluoroethylene), do not add fluorochemical monomer B, now mix fluorochemical monomer substantially all to liquefy, open stirring, and open ultraviolet lamp power about 300 watts, start to pass into oxygen (about 3.6 liters/min) at the bottom of still, also pass into Freon 13 (about 0.45 liter/min) simultaneously, temperature in the kettle controls at subzero 35 ~ subzero about 40 DEG C, react after about 8 hours and stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtain the fluorine ether oligomer transparent liquid of the molecular weight about 300 ~ 1500 of about 1.66 kilograms, proportion is about 1.63.After hydrolysis reaction, the obtained fluorine ether surface active agent containing carboxylic end group, its acid number is 70, its surface tension in water 0.1% concentration be about ~ 21 Newton/meter (N/m), there is no the good of surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid.In follow-up viton polyreaction, obtained emulsion also compares Perfluorocaprylic Acid instability.
The manufacture of comparative example 2(viton emulsion: containing Perfluorocaprylic Acid, not fluorine-containing ether carboxylic acid)
In the autoclave of about 20 liters, first the deionized water of 10L and the ammonium perfluorocaprylate of 90g is added, vacuumizing deoxygenation (until oxygen level <20ppm) in still, open stirring, temperature in the kettle is raised to about 70 DEG C, then in still, pass into the mixed gas (60:30:10 More ratio) of vinylidene and R 1216 and perfluoro methyl vinyl ether, still internal pressure reaches about 25 kilograms.5 grams of ammonium persulphates (being dissolved in advance in 500 ml waters) are added as initiator in still, started copolymer reacts, temperature in the kettle maintains 80 ~ 100 DEG C, still internal pressure is made to maintain about 25 kilograms by mixed gas in reaction process, sustained reaction reaches about 33% to emulsion solid content, after temperature in the kettle is down to room temperature, stop stirring, unreacted monomer is discharged, step-down, reactant blowing, obtains and stablizes viton emulsion, prove that the alternative Perfluorocaprylic Acid of fluorine ether carboxylic acid does polyreaction, the median size of its primary particle is about 130nm.Get sample emulsion through breakdown of emulsion, cohesion, after drying, detect this viton without fusing point, density is about 1.78g/cm
3.The embrittlement temperature of the low temperature flexibility of viton is about subzero 27 degree.Brittle temperature is not used good (comparative example 11) of fluorine ether carboxylic acid.
As can be seen here, the present invention's photochmeical reaction used and extraordinary fluorine monomer, the fluorine ether oligomer obtained has many unexpected, of great value application.Low-molecular-weight fluorine ether oligomer after hydrolysis, can make fluorine ether carboxylic acid, and its surface tension, lower than Perfluorocaprylic Acid, can be tested and prove that alternative Perfluorocaprylic Acid does fluoro containing polymers Dispersing Emulsion Polymerization.This extraordinary fluorine ether oligomer also can be made into thermostable fluorine ether oil.Very surprisingly invent described fluorine ether carboxylic acid and fluorine ether oil with this to arrange in pairs or groups together and prepare viton, experiment proves good than alone Perfluorocaprylic Acid of its resistance to low temperature of viton of gained, can obtain needed for the sealing material markets such as space flight and aviation, automobile, semi-conductor industry: the low temperature viton of ability 40 degrees below zero, this extraordinary low temperature resistant viton more can be accepted by market.
The detection method adopted in above embodiment is described below:
Density: by GB/T1033.1-2008A method test density
The mensuration of acid number: milligram potassium hydroxide needed for every gram of sample removes the numerical value (mgKOH/g sample) of middle conjunction
Surface tension: platinum around-France (Wilhelmyplatemethod)
Low temperature flexibility:
Produce LY12-CZ sheet material, be of a size of 150mm × 75mm × 1mm.Produce three specimen material samples, be of a size of 150mm × 50mm.Be pasted onto by sample in the middle part of sheet metal, entirety is positioned over cryostat (subzero 40 ± 2 DEG C or other low temperature), keeps 2 hours.In cryostat, keep material face outside, by the metal bar curved surface bending 180 of sheet metal along diameter 30mm, keep 1min.After taking-up, whether visual inspection sealing material has the situations such as crackle.
Molecular weight determination: liquid chromatograph
Viscosity measurement: adopt capillary viscosity meter (modified form Ubbelohde viscosity tube); China PetroChemical Corporation product company standard Q/SH012.4.01-86; present patent application those of ordinary skill in the field be to be understood that: the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all; any amendment of making, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of an extraordinary fluorine ether surface active agent, it is characterized in that it obtains by the following method: add in hydrolytic reaction pot deionized water and molecular-weight average 300 ~ 1500 fluorine ether oligomer, weight ratio is about 1:15 ~ 3:1, and stir intensification, temperature in the kettle is maintained until about 30 ~ 200 DEG C, the unstable end-group of fluorine ether oligomer can be hydrolyzed into carboxylic end group, reaction times was about half an hour by 8 hours, layering after reaction relief reaction solution leaves standstill, the sucking-off of upper water solution is removed, the clean deionization adding about equivalent in hydrolysis kettle again removes cleaning reaction thing, about stirring half an hour under normal temperature, again the sucking-off of upper water solution is removed, so repeat described purging method 1 ~ 3 time, reactant discharging, the obtained fluorine ether surface active agent containing carboxylic end group.
2. the preparation method of extraordinary fluorine ether surface active agent according to claim 1, is characterized in that described hydrolysis reaction temperature in the kettle preferably maintains 50 ~ 200 DEG C, and unstable end-group is acyl fluorine – COF and acyl chlorine – COCl.
3. the preparation method of extraordinary fluorine ether surface active agent according to claim 1, it is characterized in that described fluorine ether oligomer obtains by the following method: first by fluorochemical monomer A, B is with the ratio of More than 99:1 ~ 65:35, pass into the photochemical low-temp reaction still dehumidified, wherein fluorochemical monomer A: containing the tetrafluoroethylene of R 1216 0 ~ 90% More ratio of 10 ~ 100% More's ratios, fluorochemical monomer B: containing hexafluoropropylene-based alkyl oxide CF2=CFCF2-O-Rf, Rf is CnF2n+1, n=1 ~ 5: the jacket temperature of reactor will maintain below the boiling point of fluorine-containing mix monomer in advance, fluorochemical monomer is entered in still and can maintain liquid phase, general at subzero 70 degree ~ 0 degree, then stirring is opened, open ultraviolet lamp, pass in the oxygen and optional molecular weight regulator to fluorochemical monomer liquid phase dehumidified and start photochemical oxidative polymerization, the wherein purity at least 95% of oxygen, the oxygen total amount entered in photochmeical reaction still is at least 1.5 times of the total More's number of fluorochemical monomer, molecular weight regulator is fluorine-containing chloride, fluorine-containing brominated, or it is fluorine-containing containing iodine organification compound, containing 1 ~ 3 carbon, optionally there is trifluorochloromethane CF3-Cl, methyl chlorofluoride CF2Cl2, bromotrifluoromethane CF3-Br, CF3I CF3-I, trifluorochloroethylene, dichlorodifluoroethylene, the molecular weight regulator total amount entered in this photochmeical reaction still is at least 0 ~ 50% of the total More's number of fluorochemical monomer, molecular weight regulator consumption is larger, molecular weight of product is lower, photochmeical reaction is with ultraviolet catalytic, oxygen is allowed to become the Sauerstoffatom (O-) of band free radical, go to start radical polymerization, liquid phase fluorochemical monomer and the copolymerization of gas phase Sauerstoffatom, this is gas liquid reaction, gas phase oxygen demand and liquid phase fluorochemical monomer fully stir, could fully react, molecular weight regulator plays the effect of Raolical polymerizable end-blocking, reaction times half an hour by 24 hours between, fluorochemical monomer changes into the yield about 5 ~ 50% of fluorine ether oligomer, preferred yield about 10 ~ 30%, the composition of reactant is very complicated, it not single product, molecular weight distribution is 200 ~ 20000, be generically and collectively referred to as fluorine ether oligomer, its viscosity is about 1 ~ 500cPs at 25 degree of temperature, the chemical structure of described product is very complicated, because raw material composition is different, can (– CF2O-be contained) the different permutation and combination of the segment such as (-CF2CF2O-) (-CF2CF (CF3) O-) (-CF2CF (CF2OCF3) O-) (-CF2CF (CF2OC2F5) O-) (-CF2CF (CF2OC3F7) O-), its terminal group can contain-CF3,-CF2Cl,-CF2Br,-CF2I,-COF,-COCl,-COBr,-COI.
4. the preparation method of extraordinary fluorine ether surface active agent according to claim 3, it is characterized in that fluorochemical monomer A, B is preferably 95:5 ~ 80:20 with More's ratio, hexafluoropropylene-based methyl ether CF2=CFCF2-O-CF3 is preferably had containing hexafluoropropylene-based alkyl oxide, perfluoro propylene benzyl ethyl ether CF2=CFCF2-O-C2F5, hexafluoropropylene-based propyl ether CF2=CFCF2-O-C3F7 or its mixture; Fluorochemical monomer enters in still can maintain liquid phase preferably at subzero 60 degree ~ subzero 30 degree; The oxygen total amount entered in photochmeical reaction still is greater than the total More's number of fluorochemical monomer 2 times; The molecular weight regulator total amount entered in this photochmeical reaction still is preferably 1 ~ 30% of the total More's number of fluorochemical monomer.
5. the preparation method of extraordinary fluorine ether surface active agent according to claim 3, it is characterized in that the molecular-weight average of described fluorine ether oligomer is 300 ~ 1500, its viscosity is about 1 ~ 20cPs at 25 degree of temperature, be applicable to doing fluorine ether surface active agent, Perfluorocaprylic Acid substitute can be become, the molecular-weight average of described fluorine ether oligomer is more than 1500, its viscosity is about 20 ~ 500cPs at 25 degree of temperature, also be applicable to the important application doing fluorine ether oil and high temperature resistant luboil fat thereof, above product or its mixture also can as the polymerization technique of extraordinary viton auxiliary agents used, especially low temperature resistant viton, more than classification can be separated obtained fluorine ether oligomer crude product and use according to its boiling range difference with rectificating method.
6. the preparation method of extraordinary fluorine ether surface active agent according to claim 1, it is characterized in that described fluorine ether surface active agent, its acid number is between 60 to 120, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), be better than surfactivity ~ 20 Newton/meter (N/m) of Perfluorocaprylic Acid, when this kind of fluorine ether surface active agent uses in aqueous solution, can in synthesize amine salt or an alkali metal salt, an alkali metal salt is sodium salt or sylvite.
7. the preparation method of extraordinary fluorine ether surface active agent according to claim 6, is characterized in that described its acid number of fluorine ether surface active agent is preferably between 70 to 100.
8. the preparation method of extraordinary fluorine ether surface active agent according to claim 5, it is characterized in that described fluorine ether oil is obtained by following operation: the fluorine ether oligomer of molecular-weight average more than 1500 is not hydrolyzed crude product in photochmeical reaction still, carries out high temperature coupled reaction, photochmeical reaction at high temperature removes peroxide bridge and the unstable end-group of fluorine ether oligomer, such as peroxide bridge Rf-O-O-Rf is changed into Rf-O-Rf, unstable end-group as acyl fluorides-COF, acyl chlorides-COCl etc. is interrupted, cause the free radical of Rf-, the free radical of two Rf-coupling can become stable fluorinated ether chain and connects, high temperature refers between 50 to 200 degree, reaction times be about half an hour ~ 12 hours, fluorine ether oil crude product after the coupling of described preparation carries out fluoridizing (F2), reaction conditions is under oxygen condition with reactor, fluorine ether oil crude product after described coupling is passed into fluorine gas, it is kind of a gas liquid reaction, stir very crucial, also its end group of Useful UV photochemical catalysis fracture during reaction, make end group can thoroughly be fluorinated into comparatively stable end groups as-CF3, temperature of reaction is at 50 to 200 degree, reaction pressure is at 1 to 20 normal atmosphere, reaction times was about half an hour by 24 hours.
9. the preparation method of extraordinary fluorine ether surface active agent according to claim 5, it is characterized in that described extraordinary viton is obtained by following operation: in withstand voltage reactor, add deionized water, fluorine ether carboxylate is tensio-active agent, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, preferred concentration is 0.05% ~ 2.0%, radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide.
10. the preparation method of extraordinary fluorine ether surface active agent according to claim 9, it is characterized in that the low temperature resistant viton of described special type is obtained by following operation: in withstand voltage reactor, add deionized water and fluorine ether carboxylate is tensio-active agent and fluorine ether oil, after reactor deoxygenation, heated and stirred, pass into gas phase fluorochemical monomer, containing the vinylidene of More than 20% ~ 70%, 10% ~ 40% R 1216, the tetrafluoroethylene of 0% ~ 70%, all the other optional comonomers 0% ~ 40% are selected from: perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, vinyl fluoride, ethene, propylene, trifluoro-ethylene, trifluorochloroethylene, dichlorodifluoroethylene, 3, 3, any one monomer in the rare and perfluoro alkyl ethylene of 3-trifluoropropyl or exceed the combination of more than a kind of monomer, then radical initiator is added, temperature of reaction controls at 20 degree ~ 140 degree, reaction pressure controls at 1 normal atmosphere ~ 50 normal atmosphere, the average acid number of described fluorine ether carboxylic acid surfactant is 60 ~ 120, preferred average acid number is 70 ~ 100, its surface tension in water 0.1% concentration be about 13 ~ 18 Newton/meter (N/m), the concentration of described fluorine ether carboxylate in final emulsion product is 0.01% ~ 3%, preferred concentration is 0.05% ~ 2.0%, the molecular weight of described fluorine ether oil is 1500 ~ 20000, the concentration of described fluorine ether oil in final emulsion product is 0.01% ~ 3%, preferred concentration is 1% ~ 3%, described radical initiator is selected from persulphate, any one or its combination in hydrogen peroxide or organo-peroxide, described low temperature resistant viton is in 40 degrees below zero not embrittlement.
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