CN114957639B - Preparation method of poly (fluorophenyl ester) polymer with high glass transition temperature - Google Patents
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Abstract
The invention provides a preparation method of a poly (fluorophenyl ester) polymer with a high glass transition temperature, which is characterized in that a strong-polarity and high-rigidity functional group structure is introduced to improve the rotational energy barrier of a polymer chain, so that the glass transition temperature of the polymer is improved. For amorphous polymers, the working temperature of the material can be obviously improved by increasing the glass transition temperature; in addition, the polymer has wide raw material source and low material cost, and can be used for polymer film capacitors.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a preparation method of a poly (fluorophenyl) ester polymer with a high glass transition temperature.
Background
The characteristics of ultra-fast charge-discharge speed, high power density, high working voltage, low loss, good reliability and the like are important reasons that the polymer film capacitor replaces an aluminum electrolytic capacitor and becomes a key part for the alternating current-direct current conversion of the new energy automobile. At present, biaxially oriented polypropylene (BOPP) is mainly used as a dielectric material of polymer film capacitors. The material has the advantages of small dielectric loss, good processing performance, low cost, good reliability and the like, but the long-term working temperature is only 70 ℃ at most, and the higher working temperature can cause the dielectric loss to be increased sharply. Since the operating temperature of the inverter of the new energy automobile is generally over 125 ℃, a BOPP film capacitor for the new energy automobile needs to be additionally provided with a cooling system, which is very unfavorable for the light weight and the reliability of the new energy automobile. Therefore, there is a need to develop a new polymer dielectric material with high energy storage performance having high glass transition temperature and high operating temperature.
Some published data have reported that high energy storage density polymer materials mainly include ferroelectric polymers, non-ferroelectric polymers, and composite polymers. Typical ferroelectric polymers include polyvinylidene fluoride and its copolymers, with storage densities significantly greater than BOPP (IEEE tms.diector.electric.intul.2017, 24,697 polymer 2009,50, 707). But the working temperature is not more than 70 ℃, the method still cannot be applied to the high-temperature operation working condition of the new energy automobile, and the material cost is generally higher.
The non-ferroelectric polymer comprises mainstream general-purpose plastics such as polyethylene, polystyrene and the like, the working temperature of the polymer is equivalent to that of BOPP, but the energy storage density of the polymer is even smaller than that of the BOPP, and the polymer has no replacement value. The working temperature of engineering plastics such as polycarbonate can reach about 120 ℃, which can barely meet the application requirements, but the dielectric constant and the breakdown strength are small, and the comprehensive improvement of the energy storage performance after replacement is not obvious.
Among the non-ferroelectric polymers, some polymers such as polyamide, polyurea, polythiourea and the like have very high dielectric constants (mater. Chem. Phys.2021, 2100049), but the dielectric loss of polyamide and the like is very large, so that the polymer is not suitable for rapid charging and discharging application scenes of new energy automobiles and the like; and the working temperature of polyurea, polythiourea and the like does not exceed BOPP, and the method is not suitable for high-temperature working scenes.
The non-ferroelectric polymers also comprise polyether ether ketone, polyphenylene sulfide and the like, the dielectric constant of the non-ferroelectric polymers is more than 1.5 times of that of BOPP, the working temperature can reach 150-180 ℃, but the micron-sized extrusion molding process of the polymers is not mastered at home at present, so that the dielectric film suitable for capacitor packaging cannot be obtained.
The other non-ferroelectric polymers such as polyimide, polyetherimide and the like have similar problems, the working temperature can even exceed 200 ℃, and the dielectric loss factor can reach below 0.006, but the processing technology is solution casting film forming, the forming technology is not mastered at home at present, and the material cost is more than ten times of BOPP.
Therefore, there is a need to develop a polymer with a high glass transition temperature that is suitable for existing film forming processes.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a preparation method of a poly (fluorophenyl ester) polymer with high glass transition temperature, which improves the rotational energy barrier of a polymer chain by introducing a strong-polarity and high-rigidity functional group structure, thereby improving the glass transition temperature of the polymer. It is considered that for amorphous polymers, increasing the glass transition temperature can significantly increase the material operating temperature. In addition, the polymer raw material has wide source and low material cost, and can be used for polymer film capacitors.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a polyfluorophenyl ester polymer with high glass transition temperature comprises the following raw materials:
the reactant I is a diglycidyl compound containing a high-rigidity or strong polar group;
the reactant II is a fluorine-containing primary amine compound;
the reactant III is a diphenol compound containing high rigidity or strong polar groups;
the reactant IV is a compound containing active carbonyl;
the preparation method comprises the following steps:
step 1: dissolving a reactant I in a solvent, adding a reactant II, fully reacting under a heating condition, adding a reactant III, continuing to react under the protection of nitrogen, removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: and (3) taking the oligomer, adding the reactant III, dissolving the oligomer in the solvent A, dissolving the reactant IV in the solvent B, dropwise adding the solution B into the solution A at low temperature, continuing to react after dropwise adding is finished, separating and removing the solvent, and washing and drying for multiple times to obtain the high-dielectric-constant poly (fluorophenyl ester) polymer.
The invention also comprises the following technical characteristics:
specifically, the high-rigidity or strong-polarity group contained in the reactant I comprises at least one of dicyclopentadienyl, adamantyl, phenyl, biphenyl, benzocyclo, naphthyl, sulfone, ketone, ester, urethane, urea, thiourea, amide, imide and cyano;
the reactant II comprises at least one of fluorine substituted arylamine, fluorine substituted arylalkylamine and fluorine substituted alkylarylamine;
the high rigidity or strong polar group contained in the reactant III comprises at least one of dicyclopentadienyl, adamantyl, phenyl, biphenyl, various benzocyclo groups, naphthyl, sulfuryl, keto, ester, urethane, carbamido, thioureido, amido, imido and cyano;
by halogen, C, of the carbonyl carbon of reactant IV 1 -C 10 Alkoxy, haloalkoxy, aryloxy, imidazole ofAt least one of the radicals is disubstituted.
Specifically, the solvent in the step 1 is: 1,4-dioxane or toluene.
Specifically, the temperature under the heating condition of the step 1 is 50-150 ℃.
Specifically, the solvent a in the step 2 is an alkaline aqueous solvent, and includes aqueous solutions of sodium hydroxide, potassium hydroxide and ammonia with various concentrations; the solvent B is an organic solvent immiscible with water, and comprises dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, butyl acetate, toluene and xylene.
Specifically, the temperature range of the step 2 under the low-temperature condition is-15 to 5 ℃.
Specifically, the molecular weight of the poly (fluorophenyl ester) polymer is 5000-200000.
Specifically, the glass transition temperature of the poly (fluorophenyl ester) polymer is 90-210 ℃.
Specifically, the polyfluorophenyl ester polymer may be extruded and solution processed to obtain a film.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) The polymer film dielectric material is suitable for the existing general film processing equipment and processing technology, and new equipment does not need to be developed again;
(2) The polymer film dielectric prepared by the method has wide raw material sources and low material cost, and compared with the biaxial stretching polypropylene film dielectric which is widely applied at present, the working temperature is obviously improved.
Detailed Description
The invention provides a preparation method of a poly (fluorophenyl ester) polymer with high glass transition temperature, which comprises the following four raw materials:
reactant I is at least one diglycidyl compound containing high rigidity or strong polar groups;
the reactant II is at least one fluorine-containing primary amine compound;
the reactant III is at least one diphenol compound containing high rigidity or strong polar groups;
reactant IV is at least one compound containing active carbonyl;
the high rigidity or strong polar group contained in the reactant I comprises at least one of dicyclopentadienyl, adamantyl, phenyl, biphenyl, benzocyclo, naphthyl, sulfuryl, ketone group, ester group, urethane group, carbamido group, thioureido group, amido group, imide group and cyano group;
the reactant II comprises at least one of fluorine substituted arylamine, fluorine substituted arylalkylamine and fluorine substituted alkylarylamine; for example, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 3,4,5-trifluoroaniline, perfluoroaniline, 4-fluorobenzylamine, 2-fluoronaphthylamine, 4-fluoronaphthylamine, 5-fluoronaphthylamine, 8-fluoronaphthylamine.
The fluorine substitution number of the reactant II is 1-10; the aromatic ring of reactant II comprises C 4 -C 20 A conjugated ring of (a); such as benzene, naphthalene, anthracene, phenanthrene rings.
The highly rigid or strongly polar group contained in the reactant III includes at least one of biscyclopentadienyl, adamantyl, phenyl, biphenyl, various benzocyclo groups, naphthyl, sulfone groups, ketone groups, ester groups, urethane groups, urea groups, thiourea groups, amide groups, imide groups, and cyano groups.
Carbonyl carbon of reactant IV by halogen, C 1 -C 10 At least one of alkoxy, haloalkoxy, aryloxy and imidazolyl.
The preparation method specifically comprises the following steps:
step 1: dissolving a reactant I in a solvent, adding a reactant II, fully reacting under a heating condition, adding a reactant III, continuing to react under the protection of nitrogen, removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: and (3) taking the oligomer, adding the reactant III, dissolving the oligomer in the solvent A, dissolving the reactant IV in the solvent B, dropwise adding the solution B into the solution A at low temperature, continuing to react after dropwise adding is finished, separating and removing the solvent, and washing and drying for multiple times to obtain the high-dielectric-constant poly (fluorophenyl ester) polymer.
Wherein, the solvent in the step 1 is: 1,4-dioxane or toluene;
the temperature under heating in step 1 is 50 to 150 ℃.
The solvent A in the step 2 is an alkaline aqueous solvent; for example, aqueous solutions of various concentrations of sodium hydroxide, potassium hydroxide, and ammonia; the solvent B is an organic solvent which is not miscible with water; such as dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, butyl acetate, toluene, xylene;
the temperature range of the step 2 under the low temperature condition is-15 to 5 ℃.
The molecular weight of the poly (fluorophenyl ester) polymer is 5000-200000.
The glass transition temperature of the poly (fluorophenyl ester) polymer is 90-210 ℃.
The polyfluorophenyl ester polymer may be extruded and solution processed to obtain a film.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
this example provides a method for preparing a poly (fluorophenyl ester) polymer with a high glass transition temperature, comprising the steps of:
step 1: dissolving 0.125mol of bisphenol A diglycidyl ether (reactant I) in 200mL of 1, 4-dioxane, adding 0.1mol of 4-fluoroaniline (reactant II), fully reacting at 100 ℃, then adding 0.05mol of bisphenol A (reactant III), continuing to react under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
and 2, step: taking oligomer, adding 0.025mol of bisphenol A (reactant III) to dissolve in an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene (reactant IV) in 200mL of dichloromethane, dropwise adding at-15 ℃, continuing to react for 60 minutes after the dropwise adding is finished, separating and removing the solvent, and washing and drying for multiple times to obtain the polyfluorophenyl ester polymer dielectric substance, wherein the structure of the polyfluorophenyl ester polymer dielectric substance is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR, ppm): 7.28,7.17,7.02,6.85,6.71,4.60,4.05,3.95,3.36,2.64,1.72; the number average molecular weight is about 180000 and the glass transition temperature is 90 ℃.
Example 2:
this example provides a method for preparing a poly (fluorophenyl ester) polymer with a high glass transition temperature, wherein the glass transition temperature of the polymer is controlled by introducing a polar group.
Step 1: dissolving 0.125mol of 4,4 '-dihydroxy benzophenone diglycidyl ether in 200mL of toluene, adding 0.1mol of 4-fluoroaniline, fully reacting at the temperature of 100 ℃, then adding 0.05mol of 4,4' -dihydroxy benzophenone, continuing to react under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
and 2, step: taking an oligomer, adding 0.025mol of 4,4' -dihydroxybenzophenone to dissolve in an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene in 200mL of dichloromethane, dropwise adding at-10 ℃, continuing to react for 30 minutes after the dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the dielectric of the poly (fluorophenyl ester) polymer, wherein the structure of the dielectric is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR, ppm): 7.73,7.43,7.03,6.71,4.05,3.95,3.61,2.62; the number average molecular weight was about 40000 and the glass transition temperature was 125 ℃.
Example 3:
this example provides a method for preparing a poly (fluorophenyl ester) polymer with a high glass transition temperature, wherein the glass transition temperature of the polymer is controlled by further increasing the dipole moment of the polar group.
Step 1: dissolving 0.125mol of 4,4 '-dihydroxydiphenylsulfone diglycidyl ether in 200mL of toluene, adding 0.1mol of 4-fluoroaniline, fully reacting at 100 ℃, then adding 0.05mol of 4,4' -dihydroxybenzophenone, continuing to react under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: taking an oligomer, adding 0.025mol of 4,4' -dihydroxydiphenyl sulfone into the oligomer, dissolving the oligomer into an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene into 200mL of trichloromethane, dropwise adding the triphosgene at the temperature of-10 ℃, continuing to react for 30 minutes after the dropwise adding is finished, separating and removing the solvent, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer dielectric medium, wherein the structure of the poly (fluorophenyl ester) polymer dielectric medium is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR, ppm): 8.18,7.32,6.94,6.74,4.05,3.95,3.61,2.65; the number average molecular weight was about 95000 and the glass transition temperature was 160 ℃.
Example 4:
the present example provides a method for preparing a poly (fluorophenyl ester) polymer with a high glass transition temperature, wherein the glass transition temperature of the polymer is controlled by increasing polar groups on the polymer side groups.
Step 1: dissolving 0.125mol of bisphenol A diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.1mol of perfluoroaniline, fully reacting at 150 ℃, then adding 0.05mol of bisphenol A, continuously reacting under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
and 2, step: taking oligomer, adding 0.025mol of bisphenol A to dissolve in an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene in 200mL of toluene, dropwise adding at-10 ℃, continuing to react for 30 minutes after dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer dielectric substance, wherein the structure of the poly (fluorophenyl ester) polymer dielectric substance is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR 1 H-NMR, ppm): 7.28,7.17,6.85,4.05,3.95,3.36,1.72; the number average molecular weight was about 40000 and the glass transition temperature was 105 ℃.
Example 5:
the embodiment provides a preparation method of a poly (fluorophenyl ester) polymer with a high glass transition temperature, wherein the glass transition temperature of the polymer is regulated and controlled by introducing a high-rigidity group.
Step 1: dissolving 0.125mol of bisphenol Z diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.1mol of 4-fluoroaniline, fully reacting at the temperature of 80 ℃, then adding 0.05mol of bisphenol Z, continuously reacting under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: taking oligomer, adding 0.025mol of bisphenol Z into the oligomer, dissolving the bisphenol Z into an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene into 200mL of dichloromethane, dropwise adding the solution at the temperature of-5 ℃, continuing to react for 30 minutes after the dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer dielectric, wherein the structure of the poly (fluorophenyl ester) polymer dielectric is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy ( 1 H-NMR, ppm): 7.28,7.17,7.02,6.85,6.71,4.60,4.05,3.95,3.36,2.62,2.15,1.90-1.40; the number average molecular weight was about 120000 and the glass transition temperature was 135 ℃.
Example 6:
this example provides a method for preparing a poly (fluorophenyl) ester polymer with a high glass transition temperature, which is to control the glass transition temperature of the polymer by further increasing the rigidity of the group.
Step 1: dissolving 0.125mol of 4,4'- (2,2-adamantyl) diphenyl glycidyl ether in 200mL of 1, 4-dioxane, adding 0.1mol of 4-fluoroaniline, fully reacting at the temperature of 80 ℃, then adding 0.05mol of 4,4' - (2,2-adamantyl) diphenol, continuing to react under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: taking an oligomer, adding 0.025mol of 4,4'- (2,2-adamantyl) diphenol, dissolving the 4,4' - (2,2-adamantyl) diphenol into an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene into 200mL of dichloromethane, dropwise adding at 5 ℃, continuing to react for 120 minutes after the dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the dielectric of the poly (fluorophenyl ester) polymer, wherein the structure of the dielectric is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR 1 H-NMR, ppm): 7.28,7.17,7.02,6.85,6.71,4.05,3.95,3.60,2.10,1.00-1.50; the number average molecular weight was about 60000 and the glass transition temperature was 185 ℃.
Example 7:
this example provides a method for preparing a poly (fluorophenyl) ester polymer with a high glass transition temperature, wherein the glass transition temperature of the polymer is controlled by introducing a rigid structure into the main chain.
Step 1: dissolving 0.125mol of spiroindane diphenol diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.1mol of 4-fluoroaniline, fully reacting at 100 ℃, then adding 0.05mol of spiroindane diphenol, continuously reacting under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: taking an oligomer, adding 0.025mol of spiroindane diphenol into the oligomer, dissolving the spiroindane diphenol into an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene into 200mL of dichloromethane, dropwise adding the solution at the temperature of-5 ℃, continuing to react for 120 minutes after the dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the dielectric of the poly (fluorophenyl ester) polymer, wherein the structure of the dielectric is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR 1 H-NMR, ppm): 7.21,7.15,7.02,6.77,6.71,4.05,3.95,3.36,2.27,2.02,0.91; the number average molecular weight was about 25000 and the glass transition temperature was 205 ℃.
Example 8:
the embodiment provides a preparation method of a poly (fluorophenyl ester) polymer with a high glass transition temperature, wherein a rigid structure is introduced into a main chain, and the glass transition temperature of the polymer is regulated and controlled by increasing the polarity of a side group.
Step 1: dissolving 0.125mol of spiroindane diphenol diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.1mol of pentafluoroaniline, fully reacting at 120 ℃, then adding 0.05mol of spiroindane diphenol, continuously reacting under the protection of nitrogen, then removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: taking an oligomer, adding 0.025mol of spiroindane diphenol into the oligomer, dissolving the spiroindane diphenol into an aqueous solution of sodium hydroxide, dissolving 0.02mol of triphosgene into 200mL of dichloromethane, dropwise adding the solution at the temperature of-5 ℃, continuing to react for 120 minutes after the dropwise adding is finished, then separating and removing the solvent, and washing and drying for multiple times to obtain the dielectric of the poly (fluorophenyl ester) polymer, wherein the structure of the dielectric is as follows:
m and n are each independently an integer of 1 or more and 20 or less, and k is an integer of 3 or more.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR 1 H-NMR, ppm): 7.21,7.15,6.77,4.05,3.95,3.36,2.27,2.02,0.91; the number average molecular weight is about 8000 and the glass transition temperature is 210 ℃.
Claims (9)
1. A preparation method of a polyfluorophenyl ester polymer with high glass transition temperature is characterized by comprising the following raw materials:
the reactant I is a diglycidyl compound containing high rigidity or strong polar group;
the reactant II is a primary amine compound containing fluorine;
the reactant III is a diphenol compound containing high rigidity or strong polar groups;
the reactant IV is a compound containing active carbonyl;
the preparation method comprises the following steps:
step 1: dissolving a reactant I in a solvent, adding a reactant II, fully reacting under a heating condition, adding a reactant III, continuing to react under the protection of nitrogen, removing the solvent in vacuum, and washing and drying for multiple times to obtain an oligomer;
step 2: and (3) taking the oligomer, adding the reactant III, dissolving the oligomer in the solvent A, dissolving the reactant IV in the solvent B, dropwise adding the solution B into the solution A at low temperature, continuing to react after dropwise adding is finished, separating and removing the solvent, and washing and drying for multiple times to obtain the high-dielectric-constant poly (fluorophenyl ester) polymer.
2. The method for preparing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the highly rigid or strongly polar group contained in the reactant I includes at least one of biscyclopentadienyl, adamantyl, phenyl, biphenyl, benzocyclo, naphthyl, sulfone, ketone, ester, urethane, urea, thiourea, amide, imide, and cyano groups;
the reactant II comprises at least one of fluorine substituted arylamine, fluorine substituted arylalkylamine and fluorine substituted alkylarylamine;
the high rigidity or strong polar group contained in the reactant III comprises at least one of dicyclopentadienyl, adamantyl, phenyl, biphenyl, various benzo ring groups, naphthyl, sulfone group, ketone group, ester group, urethane group, carbamide group, thiourea group, amide group, imide group and cyano group;
carbonyl carbon of reactant IV by halogen, C 1 -C 10 At least one of alkoxy, haloalkoxy, aryloxy, imidazolyl.
3. The method for producing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the solvent used in step 1 is: 1,4-dioxane or toluene.
4. The method for producing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the temperature under heating in step 1 is 50 to 150 ℃.
5. The method for preparing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the solvent A of the step 2 comprises aqueous solutions of sodium hydroxide, potassium hydroxide and ammonia in various concentrations; the solvent B comprises dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, butyl acetate, toluene and xylene.
6. The method for producing a polyfluorophenyl ester polymer having a high glass transition temperature as claimed in claim 1, wherein the temperature range of the low temperature condition in step 2 is from-15 to 5 ℃.
7. The method for producing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the molecular weight of the polyfluorophenyl ester polymer is 5000 to 200000.
8. The method of producing a polyfluorophenyl ester polymer having a high glass transition temperature according to claim 1, wherein the glass transition temperature of the polyfluorophenyl ester polymer is 90 to 210 ℃.
9. The method of producing a polyfluorophenyl ester polymer having a high glass transition temperature as claimed in claim 1, wherein the polyfluorophenyl ester polymer is available in the form of a film by extrusion and solution processing.
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| US3287388A (en) * | 1963-08-07 | 1966-11-22 | Stauffer Chemical Co | Process for preparing arylfluoroformates and arylfluorothiolformates |
| US5464924A (en) * | 1994-01-07 | 1995-11-07 | The Dow Chemical Company | Flexible poly(amino ethers) for barrier packaging |
| US5962093A (en) * | 1997-10-22 | 1999-10-05 | The Dow Chemical Company | Thermally stable polyetheramines |
| CN101351506A (en) * | 2005-12-28 | 2009-01-21 | 通用电气公司 | High glass transition temperature thermoplastic articles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3287388A (en) * | 1963-08-07 | 1966-11-22 | Stauffer Chemical Co | Process for preparing arylfluoroformates and arylfluorothiolformates |
| US5464924A (en) * | 1994-01-07 | 1995-11-07 | The Dow Chemical Company | Flexible poly(amino ethers) for barrier packaging |
| US5962093A (en) * | 1997-10-22 | 1999-10-05 | The Dow Chemical Company | Thermally stable polyetheramines |
| CN101351506A (en) * | 2005-12-28 | 2009-01-21 | 通用电气公司 | High glass transition temperature thermoplastic articles |
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