CN101831074A - New type fluorine-containing copolyimide and preparation method thereof - Google Patents
New type fluorine-containing copolyimide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to new type fluorine-containing copolyimide and a preparation method thereof. The fluorine-containing copolyimide is obtained by condensation copolymerization of three monomers, i.e. the fluorine-containing copolyimide is prepared by the steps of carrying out condensation copolymerization reaction on one type of alicyclic dianhydride monomer and two types of fluorine-containing aromatic diamine monomers, or two types of the alicyclic dianhydride monomers and one type of the fluorine-containing aromatic diamine monomer in an aprotic polar solvent at low temperature, and then carrying out a thermal imidization reaction, and the new type fluorine-containing copolyimide has the advantages of high transparency, good heat resistance and the like. A fluorine-containing copolyimide film has a glass transition temperature of 200 DEG C to 350 DEG C, and is colorless and transparent; the ultraviolet absorption cutoff wavelength is between 270nm and 340 nm; the light transmittance at 450 nm is between 88% and 98%; and the fluorine-containing copolyimide film has good processing performance, and can be used as a bottom plate of a solar cell, a liquid crystal display material, a flexible transparent conductive film substrate material, an electromagnetic shielding material and the like.
Description
Technical field
The present invention relates to a kind of new type fluorine-containing copolyimide and preparation method thereof, belong to the preparation category of polymer materials in the photoelectric device.
Background technology
In photoelectric field, polymer materials, especially water white polymer materials can be used for products such as optical sensor, flexible display, solar cell.Requirement to polymer materials mainly contains optical transparence, mechanical property and resistance toheat.At present, the water white transparency polymer materials that can be used in the photoelectric field has polyethylene terephthalate (PET), polycarbonate (PC), polypropylene (PP), polyimide (PI), polypropylene diester (PPA), polytetrafluoroethylene (PTFE) etc., and wherein temperature classification is higher PET and PI.But in this big veriety of polyimide, most typical representative is by pyromellitic dianhydride and 4,4 '-diaminodiphenyl oxide synthetic line style PI, the main chain rigidity of this class PI is big, the temperature classification height, mechanical property under the high low temperature is all good, but because the rigid structure of main chain makes it not molten, insoluble, processing has brought difficulty to goods.And, also limited its application in optical field because intramolecularly or intermolecular easy formation charge transfer complex (CTC) make it often have certain color.In recent years, polyimide after fluoridizing based on studies show that of fluorinated polyimide has strengthened its solvent ability in usual vehicle (as tetrahydrofuran (THF), acetone) when keeping the polyimide high thermal stability, the processibility of material strengthens greatly, and the scattering of light that can avoid polyimide to cause owing to the hole that stays in superpolymer of dehydration in the hot-imide process.On the polyimide side chain, introduce a large amount of CF
3Behind the group, the coplanarity and the charge transfer structure of polymer molecule are destroyed, and the color of whole fluorinated polyimide material can shoal, and optical transparency strengthens greatly.Therefore, fluorinated polyimide has unique advantage and broad prospect of application in fields such as microelectronics industry, light wave communication, aerospace and gas delivery.
CN100561257 discloses a kind of fluorine-containing copolyimide that can be used as optical waveguide material, this polyimide is obtained by three monomer condenses copolymerization, promptly by two diamine monomers and a dianhydride monomer condensation copolymerization or by two dianhydride monomers and a diamine monomer condensation copolymerization, dianhydride and diamines are aromatics.The second-order transition temperature of this polyimide＞200 ℃, at the optical communication wave band 1550nm optical loss＜0.6dB/cm of place, the specific refractory power at 1550nm place is 1.5～1.6.
In document " Synthesis of copolyimide containing fluorine and naphthalene with synergizing effecton dielectric constants (Polymer Bulletin; 2005; 54; 39-46) ", the author utilizes hexafluoro bisphenol-a dianhydride and 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene (BATB) and 2 of 4-, the two two kinds of diamines copolycondensations in varing proportions of (4-amino-benzene oxygen) naphthalene (BAPN) of 7-, and the process hot-imide has obtained clear polyimides.Result of study shows, improves in the polyimide-CF
3Content can improve its transparency; Along with the BAPN ratio increases, the second-order transition temperature of copolyimide increases, but the solvability variation in organic solvent; The specific inductivity of this copolyimide is lower, reaches minimum during two kinds of mol ratios such as diamines.
In document " Copolyimides Containing Alicyclic and Fluorinated Groups:Solubility and GasSeparation Properties (Journal of Polymer Science Part B:Polymer Physics; 2005; 43 (17): 2413-2426) ", the author utilizes 4,4 '-diaminodiphenyl oxide or 2-trifluoromethyl-4,3 of 4 '-diaminodiphenyl oxide and different mol ratio example, 3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride/dicyclo [2.2.2] suffering-7-alkene-2,3,5, the copolymerization of 6-tetracarboxylic dianhydride has obtained 15 kinds and has contained alicyclic ring and CF
3The copolyimide film of group has been investigated monomer ratio and has been changed polyimide solvability, infiltrative influence.Discover: the perviousness of polyimide and deliquescent raising are interrelated, introduce alicyclic ring and contain fluorine structure and can improve its solvability and perviousness.
In document " preparation of fluorine-containing half alicyclic ring clear polyimides film and performance (investigation of materials journal; 2008; 22; 615-618) ", the author utilizes three kinds of alicyclic ring dianhydrides and two kinds of fluorine-containing aromatic diamines to react respectively, the light transmission rate that has obtained 6 kinds of 450nm places surpasses 88% clear polyimides, shown will alicyclic structure and fluoro-containing group introduce in the PI molecular structure and can keep PI inherent heat-resistant stability, and significantly reduce it in the ultraviolet-visible light district and the absorption of near infrared light communication band.
Because the preparation of copolyimide can be carried out Molecular Structure Design to the polyimide performance demands according to practical application, therefore polyimide being carried out modification by copolymerization is a kind of approach of the simplest, most convenient with the preparation new type polyimide.The copolymerization structure deteriorate the structural and regularity of molecular chain, reduced crystallinity, help the raising of processibility.If in main chain, introduce the kindliness that groups such as ehter bond, thioether bond, ketonic bond, structure of bisphenol A change main chain again, can further improve the processing characteristics of polyimide.The molecular weight and the molecular weight distribution of polyimide can be effectively regulated in three monomer condenses copolymerization, and then effectively control color, the transparency, film-forming properties, thermotolerance, solvability and the mechanical property etc. of polyimide, thereby obtain the excellent more polyimide material of over-all properties.
Therefore, new type fluorine-containing copolyimide of the present invention is to be obtained by three monomer condenses copolymerization, promptly in aprotic polar solvent, carry out the condensation copolymerization reaction at low temperatures by a kind of alicyclic ring dianhydride monomer and two kinds of fluorine-containing aromatic diamine monomers or two kinds of alicyclic ring dianhydride monomers and a kind of fluorine-containing aromatic diamine monomer, make through the hot-imide process again, have characteristics such as transparency height, good heat resistance, can be used as solar cell base plate, liquid crystal display material, flexible transparent conducting film substrate material and electromagnetic shielding material etc.
Summary of the invention
According to a kind of new type fluorine-containing copolyimide of the present invention, it is characterized in that this material is obtained by three monomer condenses copolymerization, promptly by a kind of alicyclic ring dianhydride monomer and the copolymerization of two kinds of fluorine-containing aromatic diamine monomer condenses or two kinds of alicyclic ring dianhydride monomers and the copolymerization of a kind of fluorine-containing aromatic diamine monomer condenses, the general structure of the fluorine-containing copolyimide of gained is:
Wherein,
M and n represent the polymerization degree, and m is 1～1000, and n is 1～1000, m/n=1/1000～1000/1;
According to the preparation method of fluorine-containing copolyimide of the present invention, it is characterized in that comprising the steps:
1. a kind of fluorine-containing aromatic diamine or two kinds of fluorine-containing aromatic diamine mixtures are dissolved in a certain amount of aprotic polar solvent;
2. treat under agitation to act on two kinds of alicyclic ring dianhydride mixtures or a kind of alicyclic ring dianhydride that adds certain mol proportion after fluorine-containing aromatic diamine dissolves fully, the mol ratio of fluorine-containing aromatic diamine and alicyclic ring dianhydride is 1: 0.95～1.05, the following reaction times of nitrogen protection is 15～25 hours, temperature of reaction is 0～25 ℃, obtains by weight solid content and be 10～25% even heavy-gravity polyamic acid solution;
3. will react the polyamic acid solution that 2. obtains and be coated on the clean slick sheet glass, and adopt the hot-imide method under the nitrogen protection environment, to make fluorine-containing copolyimide film through gradient increased temperature;
Wherein:
Aprotic polar solvent is selected from N, a kind of in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-or the dimethyl sulfoxide (DMSO);
The alicyclic ring dianhydride is selected from a kind of in the following dianhydride:
Fluorine-containing aromatic diamine is selected from a kind of in the following diamines:
According to the preparation method of fluorine-containing copolyimide of the present invention, it is characterized in that described aprotic polar solvent is selected from N, a kind of in dinethylformamide, the N,N-dimethylacetamide.
According to the preparation method of fluorine-containing copolyimide of the present invention, it is characterized in that described alicyclic ring dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3, and 4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) in a kind of.
Preparation method according to fluorine-containing copolyimide of the present invention, it is characterized in that described fluorine-containing aromatic diamine is selected from 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4 of 4-, 4 '-two (4-amino-2 4-trifluoromethylphenopendant) phenyl ether, 2, a kind of in two [4-(4-amino-2 4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2-.
According to the preparation method of fluorine-containing copolyimide of the present invention, the mol ratio that it is characterized in that described fluorine-containing aromatic diamine and alicyclic ring dianhydride is 1: 1.
According to the preparation method of fluorine-containing copolyimide of the present invention, the solid content that it is characterized in that described polyamic acid solution for by weight 15～20%.
According to the preparation method of fluorine-containing copolyimide of the present invention, it is characterized in that described hot-imide method is for carrying out the gradient increased temperature hot-imide in the nitrogen protection environment.
According to the preparation method of fluorine-containing copolyimide of the present invention, it is characterized in that described final imidization temperature is 200～350 ℃, the imidization time is 0.1～1 hour.
Preparation method according to fluorine-containing copolyimide of the present invention, the second-order transition temperature that it is characterized in that prepared fluorine-containing copolyimide is at 200～350 ℃, be the water white transparency shape, the uv-absorbing cutoff wavelength is at 270～340nm, and the light transmission rate at 450nm place is 88%～98%.
The gradient increased temperature hot-imide method that the present invention adopts is: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 300 ℃ of 0.5hr.
The present invention is based on introducing alicyclic structure, trifluoromethyl, a bit architecture and phenylate structure and wait the water white transparency of realizing polyimide film, and utilize copolymerization process to regulate performances such as the transparency of polyimide film and thermotolerance, obtained the good fluorine-containing copolyimide of over-all properties.
Embodiment
Embodiment 1
At first, be equipped with agitator, thermometer and nitrogen feed in the three neck reaction flasks of mouth, with 1, two (4-amino-2-4-trifluoromethylphenopendant) the benzene 2.1417g (5mmol) of 4-are dissolved among the 20.76mLDMF, treat that it dissolves the back fully and adds 1,2,3,4-tetramethylene tetracarboxylic dianhydride 0.4903g (2.5mmol) and 1,2,3,4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) 0.8307g (2.5mmol), nitrogen atmosphere stirs above-mentioned mixing solutions down, and reaction 15～25h obtains even heavy-gravity polyamic acid (PAA) solution under 0～25 ℃, PAA solid content by weight is 15wt%, limiting viscosity 1.20dL/g.This PAA solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up by following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 280 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, in 100 ℃ of loft drier after dry 2 hours fluorine-containing copolyimide film.
This fluorine-containing copolyimide film is the water white transparency shape, its salient features: second-order transition temperature is 285 ℃, and the uv-absorbing cutoff wavelength is 290nm, and the light transmission rate at 450nm place is 95%.
Embodiment 2
At first, be equipped with agitator, thermometer and nitrogen feed in the three neck reaction flasks of mouth, with 4,4 '-two (4-amino-2 4-trifluoromethylphenopendant) phenyl ether 1.3011g (2.5mmol) and 2,2 '-bis trifluoromethyl-4,4 '-benzidine 0.8006g (2.5mmol) is dissolved among the 18.48mLDMF, treat that it dissolves the back fully and adds 1,2,3,4-tetramethylene tetracarboxylic dianhydride 0.9806g (5mmol), nitrogen atmosphere stirs above-mentioned mixing solutions down, and reaction 15～25h obtains even heavy-gravity polyamic acid (PAA) solution under 0～25 ℃, PAA solid content by weight is 15wt%, limiting viscosity 1.25dL/g.This PAA solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up by following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 280 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, in 100 ℃ of loft drier after dry 2 hours fluorine-containing copolyimide film.
This fluorine-containing copolyimide film is the water white transparency shape, its salient features: second-order transition temperature is 279 ℃, and the uv-absorbing cutoff wavelength is 333nm, and the light transmission rate at 450nm place is 90%.
Embodiment 3
At first, be equipped with agitator, thermometer and nitrogen feed in the three neck reaction flasks of mouth, with 2, two [4-(4-amino-2 4-trifluoromethylphenopendant) phenyl] the HFC-236fa 3.2723g (5mmol) of 2-are dissolved among the 28.94mLDMF, treat that it dissolves the back fully and adds 1,2,4,5-hexanaphthene tetracarboxylic dianhydride 0.2242g (1mmol) and 1,2,3,4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) 1.3290g (4mmol), nitrogen atmosphere stirs above-mentioned mixing solutions down, and reaction 15～25h obtains even heavy-gravity polyamic acid (PAA) solution under 0～25 ℃, PAA solid content by weight is 15wt%, limiting viscosity 1.18dL/g.This PAA solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up by following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 280 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, in 100 ℃ of loft drier after dry 2 hours fluorine-containing copolyimide film.
This fluorine-containing copolyimide film is the water white transparency shape, its salient features: second-order transition temperature is 276 ℃, and the uv-absorbing cutoff wavelength is 303nm, and the light transmission rate at 450nm place is 92%.
Embodiment 4
At first, be equipped with agitator, thermometer and nitrogen feed in the three neck reaction flasks of mouth, with 4,4 '-two (4-amino-benzene oxygens)-3,3 ', 5.5 '-tetramethyl biphenyl 1.1211g (2mmol) and 2, two [4-(4-amino-2 4-trifluoromethylphenopendant) phenyl] the propane 1.6395g (3mmol) of 2-are dissolved among the 27.05mLDMF, treat that it dissolves the back fully and adds 1,2,3,4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) 1.6613g (5mmol), nitrogen atmosphere stirs above-mentioned mixing solutions down, and reaction 15～25h obtains even heavy-gravity polyamic acid (PAA) solution under 0～25 ℃, PAA solid content by weight is 15wt%, limiting viscosity 1.20dL/g.This PAA solution is coated on the clean sheet glass, is positioned in the loft drier that has nitrogen protection, heat up by following program: 80 ℃ of 2hrs, 120 ℃ of 1hr, 150 ℃ of 1hr, 200 ℃ of 1hr, 250 ℃ of 1hr, 280 ℃ of 0.5hr.Treat that temperature is reduced to and take out sheet glass after the room temperature and place the warm water demoulding, in 100 ℃ of loft drier after dry 2 hours fluorine-containing copolyimide film.
This fluorine-containing copolyimide film is the water white transparency shape, its salient features: second-order transition temperature is 289 ℃, and the uv-absorbing cutoff wavelength is 293nm, and the light transmission rate at 450nm place is 93%.
Claims (10)
1. new type fluorine-containing copolyimide, it is characterized in that this material is obtained by three monomer condenses copolymerization, promptly by a kind of alicyclic ring dianhydride monomer and the copolymerization of two kinds of fluorine-containing aromatic diamine monomer condenses or two kinds of alicyclic ring dianhydride monomers and the copolymerization of a kind of fluorine-containing aromatic diamine monomer condenses, the general structure of the fluorine-containing copolyimide of gained is:
Wherein,
M and n represent the polymerization degree, and m is 1～1000, and n is 1～1000, m/n=1/1000～1000/1;
-Ar
1-,-Ar
2-and-Ar-is
Kind, and
2. the preparation method of fluorine-containing copolyimide as claimed in claim 1 is characterized in that comprising the steps:
1. a kind of fluorine-containing aromatic diamine or two kinds of fluorine-containing aromatic diamine mixtures are dissolved in a certain amount of aprotic polar solvent;
2. treat under agitation to act on two kinds of alicyclic ring dianhydride mixtures or a kind of alicyclic ring dianhydride that adds certain mol proportion after fluorine-containing aromatic diamine dissolves fully, the mol ratio of fluorine-containing aromatic diamine and alicyclic ring dianhydride is 1: 0.95～1.05, the following reaction times of nitrogen protection is 15～25 hours, temperature of reaction is 0～25 ℃, obtains by weight solid content and be 10～25% even heavy-gravity polyamic acid solution;
3. will react the polyamic acid solution that 2. obtains and be coated on the clean slick sheet glass, and adopt the hot-imide method under the nitrogen protection environment, to make fluorine-containing copolyimide film through gradient increased temperature;
Wherein:
Aprotic polar solvent is selected from N, a kind of in dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-or the dimethyl sulfoxide (DMSO);
The alicyclic ring dianhydride is selected from a kind of in the following dianhydride:
Fluorine-containing aromatic diamine is selected from a kind of in the following diamines:
3. the preparation method of fluorine-containing copolyimide as claimed in claim 2 is characterized in that described aprotic polar solvent is selected from N, a kind of in dinethylformamide, the N,N-dimethylacetamide.
4. the preparation method of fluorine-containing copolyimide as claimed in claim 2 is characterized in that described alicyclic ring dianhydride is selected from 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 1,2,3, and 4-tetramethylene-symmetry (3,6-oxo bridge-1,2,3,6-tetrahydrochysene benzene-1,2-dimethyl methyl acid anhydrides) in a kind of.
5. the preparation method of fluorine-containing copolyimide as claimed in claim 2, it is characterized in that described fluorine-containing aromatic diamine is selected from 1, two (4-amino-2-4-trifluoromethylphenopendant) benzene, 4 of 4-, 4 '-two (4-amino-2 4-trifluoromethylphenopendant) phenyl ether, 2, a kind of in two [4-(4-amino-2 4-trifluoromethylphenopendant) phenyl] HFC-236fa of 2-.
6. the preparation method of fluorine-containing copolyimide as claimed in claim 2, the mol ratio that it is characterized in that described fluorine-containing aromatic diamine and alicyclic ring dianhydride is 1: 1.
7. the preparation method of fluorine-containing copolyimide as claimed in claim 2, the solid content that it is characterized in that described polyamic acid solution for by weight 15～20%.
8. the preparation method of fluorine-containing copolyimide as claimed in claim 2 is characterized in that described hot-imide method is for carrying out the gradient increased temperature hot-imide in the nitrogen protection environment.
9. the preparation method of fluorine-containing copolyimide as claimed in claim 2 is characterized in that described final imidization temperature is 200～350 ℃, and the imidization time is 0.1～1 hour.
10. the preparation method of fluorine-containing copolyimide as claimed in claim 2, the second-order transition temperature that it is characterized in that prepared fluorine-containing copolyimide is at 200～350 ℃, be the water white transparency shape, the uv-absorbing cutoff wavelength is at 270～340nm, and the light transmission rate at 450nm place is 88%～98%.
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