CN114773586A - Poly (fluorophenyl ester) polymer material and synthesis method thereof - Google Patents
Poly (fluorophenyl ester) polymer material and synthesis method thereof Download PDFInfo
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Abstract
本发明提供一种聚氟苯酯聚合物材料及其合成方法，其包含至少一个氟取代芳基侧基并且通过胺活泼氢反应引入到含碳酸二酚酯主链的聚合物中，其包含至少两个羟基侧基并通过缩水甘油基开环反应得到。由于氟取代的强诱导效应和芳基的共轭效应的协同作用，以及在主链构建碳酸二酚酯结构，该聚合物具备良好的介电和机械性能。该聚合物原料来源广泛，材料成本低廉，可用于聚合物薄膜电容器。该聚氟苯酯聚合物具有较高的分子量，能够满足薄膜成型的加工要求，同时与双轴拉伸聚丙烯相比，具有更高的介电常数，同时不引起介电损耗显著上升，旨在用于薄膜电容器的电工膜。The present invention provides a polyfluorophenyl ester polymer material and a method for synthesizing the same, which comprises at least one fluorine-substituted aryl side group and is introduced into a polymer containing a diphenol carbonate main chain through an amine active hydrogen reaction, which comprises at least one Two hydroxy pendant groups are obtained by ring-opening reaction of glycidyl group. Due to the synergistic effect of the strong inductive effect of fluorine substitution and the conjugation effect of aryl groups, as well as the construction of a diphenol carbonate structure in the main chain, the polymer has good dielectric and mechanical properties. The polymer raw material has wide sources and low material cost, and can be used for polymer film capacitors. The polyfluorophenyl ester polymer has a high molecular weight, which can meet the processing requirements of film forming. At the same time, compared with biaxially stretched polypropylene, it has a higher dielectric constant and does not cause a significant increase in dielectric loss. in electrical films used in film capacitors.
Description
Technical Field
The invention belongs to the field of high molecular materials, and relates to a polyfluorophenyl ester polymer material and a synthesis method thereof.
Background
In some scientific publications, the synthesis and properties of polymers containing pendant fluoro-substituted aryl groups, such as benzoxazine resin derivatives, are disclosed (Chen et al, ACS appl.polym.mater.2019,1,6250630); synthesis and Properties of polymers containing pendant hydroxyl groups, such as polyvinyl alcohol derivatives, phenolic resin derivatives (Lin et al, chem. Eng. J.383, 123181; Ismail et al, Molecules 2021,26, 773); the synthesis and properties of polymers comprising diphenolate carbonate backbones, such as polycarbonate derivatives (Bendler et al, eur. polym.j.2012,48,830), and in particular polymers comprising diphenolate carbonate backbones with higher dielectric constants (Bendler et al, Macromolecules 2013,46, 4024); and polymers containing both pendant hydroxyl groups and a bisphenol carbonate backbone, such as (Fontanella et al, j.polym.sci.pt.b-polym.phys.2012,50,289). CN 101877248, a bisphenol carbonate containing polymer with a high molecular weight backbone, and CN102612529, a polyester containing fluorine functionalized aromatic moieties are disclosed.
However, the above-mentioned techniques have the problems of complex synthetic reaction path, limited improvement of dielectric constant of the obtained material, etc., and the preparation method generally easily causes the breakdown strength of the material to be reduced, and the molding processability of some materials with synthetic structures is poor, so that the materials are difficult to be used for preparing polymer dielectric films with high energy storage performance.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a poly (fluorophenyl ester) polymer material and a synthesis method thereof, and aims to solve the problems that in the prior art, the synthesis reaction path is complex, the promotion of the dielectric constant of the obtained material is limited, and the material is difficult to be used for preparing a polymer dielectric film with high energy storage performance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyfluorophenyl ester polymer material, the polyfluorophenyl ester polymer has the following structural formula:
wherein R is1Is C4-C18One of fluorine-containing aryl, aralkyl and alkaryl of (a);
R2is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
R3is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
R4is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
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 invention also comprises the following technical characteristics:
specifically, the R is1Is 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4, 5-trifluorophenyl, perfluorophenyl, 4-fluorobenzyl, 2-fluoronaphthyl, 4-fluoronaphthyl or 2-fluoro-9-phenanthryl;
the R is2Is 1, 2-cyclohexyl, 1, 3-cyclohexyl, 1, 4-cyclohexyl, 4,4 '-dicyclohexyl, 4, 4' - (1, 1-methyl) dicyclohexyl, 4,4 '- (2, 2-isopropyl) dicyclohexyl, 1, 2-phenyl, 1, 3-phenyl, 1, 4-phenyl, 4, 4' -biphenyl, 4,4 '-diphenylmethyl, 4, 4' - (2, 2-diphenyl) isopropyl, 4,4 '-diphenyl ether group, 4, 4' -diphenylmethanone group, 4,4 '-diphenylsulfone group, 4, 4' - (1, 1-diphenyl) cyclohexyl, 4,4 '-diphenyldicyclopentadienyl, 4, 4' - (1, 1-diphenyl) adamantyl, 4,4 '- (1, 1-diphenyl) fluorenyl, 6' - (3,3,3 ', 3' -tetramethyl-1, 1 '-spiro) indanyl, or 5, 4' - (1,1, 3-trimethyl-3-phenyl) indanyl;
said R is3And R2The same or different;
said R is4And R2The same or different.
Specifically, the number average molecular weight of the polyfluorophenyl ester polymer is 5000-200000.
A synthetic method of a poly (fluorophenyl ester) polymer material comprises the following synthetic raw materials: reactant (I), reactant (II), reactant (III) and reactant (IV);
the reactant (I) is a compound having 2 glycidyl groups per molecule;
the reactant (II) is a compound containing fluorine and aromatic ring and having 2 amino active hydrogen per molecule;
the reactant (III) is a compound having 2 phenolic hydroxyl groups;
the reactant (IV) has the following general formula (IV):
wherein, X1And X2Are identical or different and are each independently halogen, C1-C10At least one of alkoxy, haloalkoxy, and aryloxy.
Specifically, the reactant (I) is 1, 2-cyclohexyl diglycidyl ether, 1, 3-cyclohexyl diglycidyl ether, 1, 4-cyclohexyl diglycidyl ether, 4 ' -dicyclohexyl diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1, 2-phenyl diglycidyl ether, 1, 3-phenyl diglycidyl ether, 1, 4-phenyl diglycidyl ether, 4 ' -biphenyl diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 4 ' -diphenyl ether diglycidyl ether, 4 ' -diphenyl ketone diglycidyl ether, bisphenol S diglycidyl ether, 4 ' - (1, 1-diphenyl) cyclohexyl diglycidyl ether, 4,4 '-diphenylbiscyclopentadienyl diglycidyl ether, 4' - (1, 1-diphenyl) adamantyl diglycidyl ether, 4 '- (1, 1-diphenyl) fluorenyl diglycidyl ether, 6' - (3,3,3 ', 3' -tetramethyl-1, 1 '-spiro) indanyl diglycidyl ether, or 5, 4' - (1,1, 3-trimethyl-3-phenyl) indanyl diglycidyl ether;
the reactant (II) is 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 3,4, 5-trifluoroaniline, perfluoroaniline, 4-fluorobenzylamine, 2-fluoronaphthylamine, 4-fluoronaphthylamine, 5-fluoronaphthylamine or 2-fluoro-9-aminophenanthrene;
the reactant (III) is hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol AF, 4 '-dihydroxybenzophenone, 1- (4, 4' -dihydroxyphenyl) cyclohexane, 4 '-dihydroxydiphenyldicyclopentadiene, 4' -dihydroxy (1, 1-diphenyl) adamantane, 4 '- (1, 1-diphenyl) fluorene diphenol, 6' - (3,3,3 ', 3' -tetramethyl-1, 1 '-spiro) indandiphenol or 5, 4' - (1,1, 3-trimethyl-3-phenyl) indandiphenol;
the reactant (IV) is phosgene, diphosgene, triphosgene, carbonyl diimidazole, dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, di-tert-butyl carbonate or diphenyl carbonate.
Specifically, the method comprises the following steps:
step 1: taking a reactant (I) and a reactant (II) to fully react for 6-12 hours in a system under a heating condition, then adding a reactant (III), continuing to react for 6-12 hours under the protection of nitrogen, and taking out a product after cooling to obtain an oligomer;
step 2: and (3) taking an oligomer, adding a reactant (III), dissolving the oligomer in a solvent (A) to obtain a solution A, dissolving a reactant (IV) in a solvent (B) to obtain a solution B, dropwise adding the solution B into the solution A at a low temperature, continuing to react for 30-120 minutes after the dropwise adding is finished, separating out the solution through petroleum ether, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer.
Specifically, the system of the step 1 is a solvent-containing system or a solvent-free system; wherein, the solvent for the solvent system is an organic solvent capable of sufficiently dissolving the reactant (I) and the reactant (II), and comprises acetone, butanone, dichloromethane, chloroform, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide or dimethyl sulfoxide.
Specifically, the temperature range under the heating condition of the step 1 is 50-150 ℃.
Specifically, the solvent (a) in step 2 is an alkaline aqueous solvent, including aqueous solutions of sodium hydroxide, potassium hydroxide or ammonia with various concentrations;
the solvent (B) of step 2 is a water-immiscible organic solvent including dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, butyl acetate, toluene or xylene.
Specifically, the temperature range of the step 2 under the low-temperature condition is-15-5 ℃.
Compared with the prior art, the invention has the beneficial technical effects that:
the poly (fluorophenyl fluoride) polymer material comprises at least one fluorine-substituted aryl side group and is introduced into a polymer containing a diphenol carbonate main chain through an amine active hydrogen reaction, and the poly (fluorophenyl fluoride) polymer material comprises at least two hydroxyl side groups and is obtained through a glycidyl ring-opening reaction; due to the synergistic effect of the strong induction effect of fluorine substitution and the conjugate effect of aryl and the construction of a carbonate structure on a main chain, the polymer has good dielectric and mechanical properties.
Compared with the dielectric medium widely adopted by the existing film capacitor, the dielectric constant is higher, the dielectric loss is not obviously increased, and the processing can meet the film forming requirement; specifically, the poly (fluorophenyl ester) polymer has a relatively high molecular weight, can meet the processing requirements of film forming, has a relatively high dielectric constant compared with biaxially stretched polypropylene, does not cause significant increase of dielectric loss, and is intended to be used for an electrical film of a film capacitor.
The preparation method is easy, the raw material source is wide, the material cost is low, and the preparation method can be used for polymer film capacitors.
Detailed Description
The invention provides a poly (fluorophenyl ester) polymer material and a synthesis method thereof, wherein the structural formula of the poly (fluorophenyl ester) polymer is as follows:
wherein R is1Is C4-C18At least one of a fluorine-containing aryl group, aralkyl group, and alkaryl group; for example: 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 3,4, 5-trifluorophenyl group, perfluorophenyl group, 4-fluorobenzyl group, 2-fluoronaphthyl group, 4-fluoronaphthyl group, 2-fluoro-9-phenanthryl group;
R2is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkarylAt least one of (a); for example, 1, 2-cyclohexyl, 1, 3-cyclohexyl, 1, 4-cyclohexyl, 4,4 '-dicyclohexyl, 4, 4' - (1, 1-methyl) dicyclohexyl, 4,4 '- (2, 2-isopropyl) dicyclohexyl, 1, 2-phenyl, 1, 3-phenyl, 1, 4-phenyl, 4, 4' -biphenyl, 4,4 '-diphenylmethyl, 4, 4' - (2, 2-diphenyl) isopropyl, 4,4 '-diphenyl ether group, 4, 4' -diphenylmethanone group, 4,4 '-diphenylsulfone group, 4, 4' - (1, 1-diphenyl) cyclohexyl, 4,4 '-diphenyldicyclopentadienyl, 4, 4' - (1, 1-diphenyl) adamantyl, 4,4 '- (1, 1-diphenyl) fluorenyl, 6' - (3,3,3 ', 3' -tetramethyl-1, 1 '-spiro) indanyl, 5, 4' - (1,1, 3-trimethyl-3-phenyl) indanyl;
R3is C6-C20At least one of alkyl, aryl, aralkyl and alkaryl containing or not containing nitrogen, oxygen and sulfur; for example with R2The same or different;
R4is C6-C20At least one of alkyl, aryl, aralkyl and alkaryl containing or not containing nitrogen, oxygen and sulfur; for example with R2The same or different;
wherein 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;
specifically, the number average molecular weight of the polyfluorophenyl ester polymer is 5000-200000.
The invention also provides a synthetic method of the polyfluorophenyl ester polymer material, which comprises the following synthetic raw materials: reactant (I), reactant (II), reactant (III) and reactant (IV);
the reactant (I) is at least one compound having 2 glycidyl groups per molecule, for example
1, 2-cyclohexyl diglycidyl ether, 1, 3-cyclohexyl diglycidyl ether, 1, 4-cyclohexyl diglycidyl ether, 4 ' -dicyclohexyl diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1, 2-phenyl diglycidyl ether, 1, 3-phenyl diglycidyl ether, 1, 4-phenyl diglycidyl ether, 4 ' -biphenyl diglycidyl ether, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 4 ' -diphenyl ether diglycidyl ether, 4 ' -diphenyl ketone diglycidyl ether, bisphenol S diglycidyl ether, 4 ' - (1, 1-diphenyl) cyclohexyl diglycidyl ether, 4 ' -diphenyl biscyclopentadienyl diglycidyl ether, 1,4 ' -cyclohexyl diglycidyl ether, 4 ' -phenyl diglycidyl ether, 4 ' -biphenyl diglycidyl ether, 4-phenyl diglycidyl ether, and mixtures thereof, 4,4 ' - (1, 1-diphenyl) adamantyl diglycidyl ether, 4 ' - (1, 1-diphenyl) fluorenyl diglycidyl ether, 6 ' - (3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spiro) indanyl diglycidyl ether, or 5,4 ' - (1,1, 3-trimethyl-3-phenyl) indanyl diglycidyl ether;
the reactant (II) is at least one fluorine-and aromatic ring-containing compound having 2 amino active hydrogens per molecule, for example, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 3,4, 5-trifluoroaniline, perfluoroaniline, 4-fluorobenzylamine, 2-fluoronaphthylamine, 4-fluoronaphthylamine, 5-fluoronaphthylamine, 2-fluoro-9-aminophenanthrene;
the reactant (III) is at least one compound having 2 phenolic hydroxyl groups, for example, hydroquinone, bisphenol a, bisphenol S, bisphenol F, bisphenol AF, 4 '-dihydroxybenzophenone, 1- (4, 4' -dihydroxyphenyl) cyclohexane, 4 '-dihydroxydiphenyldicyclopentadiene, 4' -dihydroxy (1, 1-diphenyl) adamantane, 4 '- (1, 1-diphenyl) fluorene diphenol, 6' - (3,3,3 ', 3' -tetramethyl-1, 1 '-spiro) indandiol or 5, 4' - (1,1, 3-trimethyl-3-phenyl) indandiol;
said reactant (IV) is at least one compound having the general formula (IV) below:
wherein, X1And X2Are identical or different and are each independently halogen, C1-C10For example phosgene, diphosgene, triphosgene, carbonyldiimidazole, dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, di-tert-butyl carbonate, diphenyl carbonate.
The synthesis method comprises the following steps:
step 1: taking a reactant (I) and a reactant (II) to fully react for 6-12 hours in a system under a heating condition, then adding a reactant (III), continuing to react for 6-12 hours under the protection of nitrogen, and taking out a product after cooling to obtain an oligomer;
and 2, step: and (3) taking an oligomer, adding a reactant (III), dissolving the oligomer in a solvent (A) to obtain a solution A, dissolving a reactant (IV) in a solvent (B) to obtain a solution B, dropwise adding the solution B into the solution A at a low temperature, continuing to react for 30-120 minutes after the dropwise adding is finished, separating out the solution through petroleum ether, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer.
Wherein, the system in the step 1 is a solvent-containing system or a solvent-free system; among the solvents that can be selected for the solvent system are organic solvents capable of sufficiently dissolving the reactant (I) and the reactant (II), such as acetone, butanone, dichloromethane, chloroform, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, toluene, xylene, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide;
the temperature range under the heating condition in the step 1 is 50-150 ℃.
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) in the step 2 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-15-5 ℃.
The polyfluorophenyl ester polymer obtained by the above synthesis method can be extruded and processed into a film through a solution.
The following embodiments are given as examples of the present invention, 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 included in the protection scope of the present invention.
Example 1:
this example provides a poly (fluorophenyl ester) polymer material, which has the following specific structure, wherein R1Is 4-fluorophenyl, R2、R3、R44, 4' -isopropyldiphenyl:
the embodiment also provides a synthesis method of the polyfluorophenyl ester polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.05mol of 4-fluoroaniline, fully reacting at 120 ℃, then adding 0.10mol of bisphenol A, continuing to react under the protection of nitrogen, then adding 300mL of petroleum ether for precipitation, and washing and drying for multiple times to obtain an oligomer;
step 2: and (2) taking an oligomer, adding 0.05mol of bisphenol A, dissolving the oligomer in an aqueous solution of sodium hydroxide, dissolving 0.04mol of triphosgene in 200mL of dichloromethane, dropwise adding the solution at the temperature of-15 ℃, continuing to react for 60 minutes after the dropwise adding is finished, then adding 300mL of petroleum ether, precipitating, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer material.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR1H-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, the dielectric constant is 4.5 under power frequency, and the dielectric loss factor is 0.006.
Example 2:
this example provides a polyfluorophenyl ester polymeric material having a modified number of fluorine substitutions, R1Is 3,4, 5-trifluorophenyl, R2、R3、R4Is 4, 4' -isopropyl diphenyl, and has the following specific structure:
the embodiment also provides a synthesis method of the polyfluorophenyl ester polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 250mL of 1, 4-dioxane, adding 0.05mol of 3,4, 5-trifluoroaniline, fully reacting at the temperature of 150 ℃, then adding 0.10mol of bisphenol A, continuing to react under the protection of nitrogen, then adding 400mL of petroleum ether, separating out, and washing and drying for multiple times to obtain an oligomer;
step 2: and (2) taking an oligomer, adding 0.05mol of bisphenol A, dissolving the oligomer in an aqueous solution of potassium hydroxide, dissolving 0.04mol of triphosgene in 200mL of dichloromethane, dropwise adding the solution at 0 ℃, continuing to react for 60 minutes after the dropwise adding is finished, then adding 300mL of petroleum ether, separating out, washing and drying for multiple times, and obtaining the poly (fluorophenyl ester) polymer material.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy (1H-NMR, ppm): 7.28,7.17,6.58,4.60,4.05,3.95,3.36,2.70, 1.73; the number average molecular weight is about 120000, the dielectric constant is 4.7 at power frequency, and the dielectric loss factor is 0.006.
Example 3:
this example provides a polyfluorophenyl ester polymeric material having a modified fluoro-substituted aryl group, R1Is 4-fluoronaphthyl, R2、R3、R4Is 4, 4' -isopropyl diphenyl, and has the following specific structure:
the embodiment also provides a synthesis method of the polyfluorophenyl ester polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 250mL of N, N' -dimethylformamide, adding 0.05mol of 4-fluoronaphthylamine, fully reacting at 100 ℃, then adding 0.10mol of bisphenol A, continuing to react under the protection of nitrogen, then adding 400mL of petroleum ether, separating out, and washing and drying for multiple times to obtain an oligomer;
and 2, step: and (2) taking the oligomer, adding 0.05mol of bisphenol A, dissolving the oligomer in an ammonia water solution, dissolving 0.04mol of triphosgene in 200mL of dichloromethane, dropwise adding the solution at the temperature of-10 ℃, continuing to react for 60 minutes after the dropwise adding is finished, then adding 300mL of petroleum ether, precipitating, washing and drying for multiple times, and obtaining the poly (fluorophenyl ester) polymer material.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR1H-NMR, ppm): 8.50,8.05,7.48,7.28,7.17,7.00,6.85,4.05,3.95,3.36,2.65, 1.72; the number average molecular weight is about 60000, the dielectric constant is 4.8 at power frequency, and the dielectric loss factor is 0.01.
Example 4:
this example provides a polyfluorophenyl ester polymeric material having a modified glycidyl reactant, R1Is 4-fluorophenyl, R2Is 4, 4' -benzophenone group, R3、R4Is 4, 4' -isopropyl diphenyl, and has the following specific structure:
the embodiment also provides a synthesis method of the polyfluorophenyl ester polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of benzophenone diglycidyl ether in 250mL of toluene, adding 0.05mol of 4-fluoroaniline, fully reacting at the temperature of 80 ℃, then adding 0.10mol of bisphenol A, continuing to react under the protection of nitrogen, then adding 400mL of petroleum ether for precipitation, and washing and drying for multiple times to obtain an oligomer;
step 2: and (2) taking an oligomer, adding 0.05mol of bisphenol A, dissolving the oligomer in an aqueous solution of sodium hydroxide, dissolving 0.04mol of triphosgene in 200mL of dichloromethane, dropwise adding the solution at 5 ℃, continuing to react for 60 minutes after the dropwise adding is finished, then adding 500mL of petroleum ether, precipitating, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer material.
The dielectric Polyfluorophenyl ester Polymer obtained in this example was analyzed by NMR1H-NMR, ppm): 7.73,7.28,7.17,7.01,6.85,6.71,4.05,3.95,3.38,2.63, 1.72; the number average molecular weight is about 30000, the dielectric constant is 5.1 at power frequency, and the dielectric loss factor is 0.005.
Example 5:
this example provides a polyfluoro compoundPhenyl ester polymeric material having a step change in phenolic hydroxyl compound, R1Is 4-fluorophenyl, R2Is 4, 4' -isopropyldiphenyl, R3、R4Is 4, 4' -cyclohexyl diphenyl, and has the following specific structure:
the embodiment also provides a synthesis method of the poly (fluorophenyl ester) polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 250mL of dioxane, adding 0.05mol of 4-fluoroaniline, fully reacting at the temperature of 50 ℃, then adding 0.10mol of 1,1- (4, 4' -dihydroxyphenyl) cyclohexane, continuing to react under the protection of nitrogen, then adding 400mL of petroleum ether, separating out, and washing and drying for multiple times to obtain an oligomer;
step 2: taking oligomer, adding 0.05mol of 1,1- (4, 4' -dihydroxyphenyl) cyclohexane, dissolving the oligomer in an aqueous solution of sodium hydroxide, dissolving 0.04mol of triphosgene in 200mL of dichloromethane, dropwise adding the solution at the temperature of-5 ℃, continuing to react for 30 minutes after the dropwise adding is finished, adding 400mL of petroleum ether, precipitating, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer material.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy (1H-NMR, ppm): 7.28,7.17,7.02,6.85,6.71,4.60,4.05,3.95,3.36,2.62,2.15,1.90,1.72,1.53,1.46, 1.43; the number average molecular weight is about 120000, the dielectric constant is 4.2 under power frequency, and the dielectric loss factor is 0.002.
Example 6:
this example provides a polyfluorophenyl ester polymeric material having a step change in the diphenol hydroxyl compound, R1Is 4-fluorophenyl, R2Is 4, 4' -isopropyldiphenyl, R3、R4Is 4, 4' -diphenyl ketone group, and has the following specific structure:
the embodiment also provides a synthesis method of the polyfluorophenyl ester polymer material, which comprises the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 250mL of dioxane, adding 0.05mol of 4-fluoroaniline, fully reacting at the temperature of 80 ℃, then adding 0.10mol of 4, 4' -dihydroxy benzophenone, continuing to react under the protection of nitrogen, then adding 400mL of petroleum ether, separating out, and washing and drying for multiple times to obtain an oligomer;
and 2, step: and (2) adding 0.05mol of 4, 4' -dihydroxybenzophenone into the oligomer, dissolving the oligomer in an aqueous solution of sodium hydroxide, dissolving 0.04mol of triphosgene into 200mL of dichloromethane, dropwise adding the solution at the temperature of 5 ℃, continuing to react for 45 minutes after the dropwise adding is finished, adding 400mL of petroleum ether, precipitating, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer material.
The dielectric material of the polyfluorophenyl ester polymer obtained in this example was measured for hydrogen nuclear magnetic resonance spectroscopy (1H-NMR, ppm): 7.73,7.43,7.28,7.01,6.85,6.74,4.30,4.05,3.95,3.38,2.64, 1.72; the number average molecular weight is about 10000, the dielectric constant is 5.2 under power frequency, and the dielectric loss factor is 0.004.
Example 7:
this example provides a polyfluorophenyl ester polymer material having the same structure as in example 1.
This example also provides a method for synthesizing a poly (fluorophenyl ester) polymer material, in which the reactant (IV) is changed compared to example 1, including the following steps:
step 1: dissolving 0.10mol of bisphenol A diglycidyl ether in 200mL of 1, 4-dioxane, adding 0.05mol of 4-fluoroaniline, fully reacting at 100 ℃, then adding 0.10mol of bisphenol A, continuing to react under the protection of nitrogen, then adding 300mL of petroleum ether, separating out, and washing and drying for multiple times to obtain an oligomer;
step 2: and (2) adding 0.05mol of bisphenol A into the oligomer, dissolving the oligomer in an aqueous solution of sodium hydroxide, dissolving 0.04mol of carbonyldiimidazole in 200mL of trichloromethane, dropwise adding the mixture at the temperature of minus 10 ℃, continuing to react for 60 minutes after the dropwise adding is finished, then adding 300mL of petroleum ether to precipitate, and washing and drying the mixture for multiple times to obtain the poly (fluorophenyl ester) polymer material.
Claims (10)
1. A polyfluorophenyl ester polymer material is characterized in that the polyfluorophenyl ester polymer has the following structural formula:
wherein R is1Is C4-C18One of fluorine-containing aryl, aralkyl and alkaryl of (a);
R2is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
R3is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
R4is C6-C20With or without nitrogen, oxygen, sulfur, aryl, aralkyl, alkaryl;
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.
2. The polyfluorophenyl ester polymeric material of claim 1, wherein R is R1Is 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,4, 5-trifluorophenyl, perfluorophenyl, 4-fluorobenzyl, 2-fluoronaphthyl, 4-fluoronaphthyl or 2-fluoro-9-phenanthryl;
the R is2Is 1, 2-cyclohexyl, 1, 3-cyclohexyl, 1, 4-cyclohexyl, 4,4 ' -dicyclohexyl, 4,4 ' - (1, 1-methyl) dicyclohexyl, 4,4 ' - (2, 2-isopropyl) dicyclohexyl, 1, 2-phenyl, 1, 3-phenyl, 1, 4-phenyl, 4,4 ' -biphenyl, 4,4 ' -diphenylmethyl, 4,4 ' - (2, 2-diphenyl) isopropyl, 4,4 ' -diphenyl ether group, 4,4 ' -diphenylmethanone group, 4,4 ' -diphenylsulfone group, 4,4 ' - (1, 1-diphenyl) cyclohexyl, 4,4 ' -diphenylsulfone groupBiscyclopentadienyl, 4 ' - (1, 1-diphenyl) adamantyl, 4 ' - (1, 1-diphenyl) fluorenyl, 6 ' - (3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spiro) indanyl, or 5,4 ' - (1,1, 3-trimethyl-3-phenyl) indanyl;
said R is3And R2The same or different;
said R is4And R2The same or different.
3. The polyphenylphluoride polymer material according to claim 1, wherein the number average molecular weight of the polyphenylphluoride polymer is 5000-.
4. A method for synthesizing a polyfluorophenyl ester polymeric material as claimed in any one of claims 1 to 3, wherein the raw materials for synthesis comprise: reactant (I), reactant (II), reactant (III) and reactant (IV);
the reactant (I) is a compound having 2 glycidyl groups per molecule;
the reactant (II) is a compound containing fluorine and aromatic ring and having 2 amino active hydrogen per molecule;
the reactant (III) is a compound having 2 phenolic hydroxyl groups;
the reactant (IV) has the following general formula (IV):
wherein X1And X2Are identical or different and are each independently halogen, C1-C10At least one of alkoxy, haloalkoxy, and aryloxy.
5. The method of synthesizing a polyfluorophenyl ester polymer material according to claim 4, wherein the reactant (I) is 1, 2-cyclohexyldiglycidyl ether, 1, 3-cyclohexyldiglycidyl ether, 1, 4-cyclohexyldiglycidyl ether, 4 '-dicyclohexyldiglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1, 2-phenyldiglycidyl ether, 1, 3-phenyldiglycidyl ether, 1, 4-phenyldiglycidyl ether, 4' -biphenyldiglycidyl ether, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 4 '-diphenylether diglycidyl ether, 4' -diphenylketone diglycidyl ether, bisphenol S diglycidyl ether, 4,4 ' - (1, 1-diphenyl) cyclohexyl diglycidyl ether, 4 ' -diphenylbiscyclopentadienyl diglycidyl ether, 4 ' - (1, 1-diphenyl) adamantyl diglycidyl ether, 4 ' - (1, 1-diphenyl) fluorenyl diglycidyl ether, 6 ' - (3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spiro) indanyl diglycidyl ether, or 5,4 ' - (1,1, 3-trimethyl-3-phenyl) indanyl diglycidyl ether;
the reactant (II) is 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 3,4, 5-trifluoroaniline, perfluoroaniline, 4-fluorobenzylamine, 2-fluoronaphthylamine, 4-fluoronaphthylamine, 5-fluoronaphthylamine or 2-fluoro-9-aminophenanthrene;
the reactant (III) is hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol AF, 1- (4,4 ' -dihydroxyphenyl) cyclohexane, 4 ' -dihydroxydiphenyl dicyclopentadiene, 4 ' -dihydroxy (1, 1-diphenyl) adamantane, 4 ' - (1, 1-diphenyl) fluorene diphenol, 6 ' - (3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spiro) indandiphenol or 5,4 ' - (1,1, 3-trimethyl-3-phenyl) indandiphenol;
the reactant (IV) is phosgene, diphosgene, triphosgene, carbonyl diimidazole, dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, di-tert-butyl carbonate or diphenyl carbonate.
6. The method of synthesizing a polyfluorophenyl ester polymeric material of claim 5, comprising the steps of:
step 1: taking a reactant (I) and a reactant (II) to fully react for 6-12 hours in a system under a heating condition, then adding a reactant (III), continuing to react for 6-12 hours under the protection of nitrogen, and taking out a product after cooling to obtain an oligomer;
step 2: and (3) taking an oligomer, adding a reactant (III), dissolving the oligomer in a solvent (A) to obtain a solution A, dissolving a reactant (IV) in a solvent (B) to obtain a solution B, dropwise adding the solution B into the solution A at a low temperature, continuing to react for 30-120 minutes after the dropwise adding is finished, separating out the solution through petroleum ether, and washing and drying for multiple times to obtain the poly (fluorophenyl ester) polymer.
7. The method of synthesizing a polyfluorophenyl ester polymeric material of claim 6, wherein the system of step 1 is a solvent-containing system or a solvent-free system; wherein, the solvent for the solvent system is an organic solvent capable of sufficiently dissolving the reactant (I) and the reactant (II), and comprises acetone, butanone, dichloromethane, chloroform, tetrahydrofuran, dioxane, ethyl acetate, butyl acetate, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide or dimethyl sulfoxide.
8. The method for synthesizing a polyfluorophenyl ester polymer material according to claim 6, wherein the temperature range under heating in step 1 is 50 to 150 ℃.
9. The method for synthesizing a polyfluorophenyl ester polymeric material according to claim 6, wherein the solvent (A) of the step 2 is an alkaline aqueous solvent comprising aqueous solutions of sodium hydroxide, potassium hydroxide or ammonia in various concentrations;
the solvent (B) in step 2 is a water-immiscible organic solvent comprising dichloromethane, trichloromethane, tetrachloromethane, ethyl acetate, butyl acetate, toluene or xylene.
10. The method for synthesizing a polyfluorophenyl ester polymer material according to claim 6, wherein the temperature range of the low temperature condition of step 2 is-15 to 5 ℃.
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