CN105085912A - Transparent polyesterimide resin and preparing method thereof - Google Patents
Transparent polyesterimide resin and preparing method thereof Download PDFInfo
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Abstract
The invention discloses transparent polyesterimide resin and a preparing method conducted through condensation polymerization of a di(3,4-dimethylbenzene anhydride) phenyl terephthalate monomer and a binary primary amine monomer. In the design of dianhydride, the electron affinity of the dianhydride is reduced, formation of charge transfer complexes in polyesterimide molecules and among the molecules is inhibited, and therefore the transparent performance is improved. The glass transformation temperature of the polyesterimide resin is 200-350 DEG C, the light transmissivity at the position of 400 nm is 70%-90%, water absorption of a thin film is smaller than 0.5%, and the transparent polyesterimide resin has good application prospects in the fields of flexible substrate materials, flexible transparent conduction film substrate materials, liquid crystal display materials and the like of solar batteries.
Description
Technical field
The present invention relates to polyimide and preparation field thereof, be specifically related to a kind of transparent polyester imide resin and preparation method thereof.
Background technology
Polyimide is topmost kind in the aromatic heterocyclic copolymer grown up nearly half a century, also be the family macromolecule material that use temperature is the highest, there is the over-all properties that physical strength is high, high temperature resistant, chemically stable, creep resistance etc. are very excellent, at Aeronautics and Astronautics, electrically, be widely used in machinery, microelectronics, chemical industry etc.
Recently along with the development of new high-tech industry, the demand of the polyimide of heat-resisting to height, the high printing opacities of optical field such as photoconduction, waveguide and liquid-crystal display is more and more urgent, because the transparent polyimide having high thermal resistance and high light transmittance concurrently can be applied to some other non-serviceable fields of transparent resin, such as: computer control shows, liquid-crystal display, the cover of the opticses such as electronic indicating meter, the substrate of Polarizer, solar cell and plastic lens etc.But traditional polyimide film generally presents faint yellow or Vandyke brown, greatly limit the further application of polyimide in photoelectric material, its major cause to be present in main polymer chain in the dianhydride residue that alternately occurs in the electron attraction of carbonyl and the molecule produced to electronic action of diamines residue and the formation of intermolecular charge transfer complex.Therefore can by changing molecular structure, exploitation can be used for flexible solar battery base plate, the thermostable transparent polyimide resin material in the fields such as Flexible Displays or illumination base plate.
For full aromatic polyimide, the method of current its color of reduction is mainly: (1) introduces containing fluoro substituents in polyimide molecule structure, because fluorine atom has very large electronegativity, the conjugation of electronic cloud can be cut off, suppress the formation of charge transfer complex.As the transparent polyimide film material LaRC of NASA's exploitation
tM-CP1 and LaRC
tM-CP2 is that see US Patent No. 4603061 and US4595548, but this dianhydride monomer is expensive with hexafluorodianhydride (6FDA).(2) by reducing the electron affinity of dianhydride and diamines, the formation of charge transfer complex is suppressed.Clear polyimides prepared by two ether dianhydrides that such as Chinese patent CN102911359 discloses a kind of low electron affinity, but due to the introducing of soft segment ehter bond in this monomer, cause the second-order transition temperature of prepared polyimide to reduce.
In order to overcome this problem, the diester dianhydride that many researchists attempt adopting trimellitic acid 1,2-anhydride and various diphenol to prepare is to synthesize corresponding polyester-imide, as periodical Macromol.Mater.Eng.2011,296, report the contrast experiment of polyetherimide and polyester-imide in 1002 – 1017, can see compared to polyetherimide, polyester-imide improves the second-order transition temperature of polymkeric substance, but properties of transparency reduces greatly, need to be improved further.
Summary of the invention
Technical purpose of the present invention is for above-mentioned prior art, provides a kind of transparent polyester imide resin, has the excellent advantage such as optical transmittance, good thermotolerance, lower water-intake rate.
A kind of transparent polyester imide resin, described transparent polyester imide resin has following structural formula:
Wherein, Ar is binary primary amine monomer residue, n to be the quantity of repeating unit be greater than 0 integer.
Described Ar can be selected from following groups one or more:
Wherein, end two horizontal lines "-" represent the connecting key of nitrogen-atoms in Ar group and repeating unit, and do not represent methyl.
As preferably, described Ar can be selected from following groups one or more:
As further preferred, described Ar can be selected from the one in following groups:
Polyesterimide resin of the present invention presents transparence, and second-order transition temperature can be 200 DEG C ~ 350 DEG C, and the light transmission rate at 400nm place is 70% ~ 90%, and water-intake rate is less than 0.5%.In view of these performances, transparent polyesterimide resin of the present invention can have good application prospect in association areas such as the flexible substrate material of solar cell, flexible transparent conducting film substrate material, liquid crystal display materials.
Present invention also offers a kind of preparation method of described transparent polyester imide resin, have easy and simple to handle, be easy to the advantages such as control.
The preparation method of described transparent polyester imide resin, is obtained by polycondensation by terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester and binary primary amine monomer.
The structural formula of described terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester is as follows:
The preparation method of described transparent polyester imide resin, is specially:
(1) binary primary amine monomer is added in the polar aprotic solvent of nitrogen or protection of inert gas, stirring adds terephthalic acid two (3 after making it dissolve completely, 4-dicarboxylic acid anhydride) phenyl ester, stirring reaction 12 hours ~ 48 hours, obtains the polyesteramide acid solution of clear viscous;
(2) adopt hot imidization method or chemical imidization method that polyesteramide acid solution is prepared into polyester-imide solution, dry, obtained transparent polyester imide resin.
Described hot imidization method comprises: dry after polyesteramide acid solution being applied as film, obtained transparent polyester imide resin;
Described chemical imidization method comprises: the mixed solution adding diacetyl oxide and pyridine in polyesteramide acid solution, continue stirring reaction 12 hours ~ 48 hours, obtain polyester-imide solution, polyester-imide solution is poured in precipitation agent, fully washing, drying after collecting precipitation, obtained transparent polyester imide resin.
Described polar aprotic solvent can select in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone etc. one or more.
Described precipitation agent can select ethanol, methyl alcohol, acetone, water.
The rare gas element that described rare gas element selects this area conventional, as argon gas etc.
Described terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester and the mol ratio of binary primary amine monomer are generally 1:0.9 ~ 1.1.
Described binary primary amine monomer can be selected from 3,3 '-diaminodiphenylsulfone(DDS), 4,4′ diaminodiphenyl sulfone, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4，4′-diaminodipohenyl ether, two (4-aminophenyl) HFC-236fa of 2,2-, two (3-aminophenyl) HFC-236fa of 2,2-, two (3-amino-benzene oxygen) benzene of 1,3-, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 1,3-, two (5-amino-3-4-trifluoromethylphenopendant) benzene of 1,3-, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, one or more in 3,3-bis-(4-aminophenyl)-3H-isobenzofuranone.
Compared with prior art, the Sauerstoffatom of the ester bond in diester dianhydride is connected with phthalic anhydride by the present invention in the design of dianhydride monomer, change the situation that carbonyl is in the past connected with phthalic anhydride, can on the basis retaining original ester bond, greatly reduce the electron affinity of this dianhydride, suppress charge transfer complex in polyester-imide molecule and intermolecular formation, improve properties of transparency, reduce the water-intake rate of film; The reservation of ester bond simultaneously makes prepared polyester-imide increase than original polyetherimide on second-order transition temperature.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1
In the present embodiment, transparent polyester imide resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 4 of 1.7230g (4.0mmol); 4 '-bis-(3-amino-benzene oxygen) sulfobenzide and 16 milliliters of N; N-N,N-DIMETHYLACETAMIDE adds in 50mL reaction flask; stirring at room temperature; treat 4; after 4 '-bis-(3-amino-benzene oxygen) sulfobenzide dissolves completely; add the terephthalic acid two (3 of 1.8334g (4.0mmol) again; 4-dicarboxylic acid anhydride) phenyl ester; continuing stirring at room temperature 24 hours, the polyesteramide acid solution of obtained thickness, is then 10% by solution dilution to concentration expressed in percentage by weight.Then add the mixed solution of 4mL diacetyl oxide and 2mL pyridine, continue stirring at room temperature 24 hours, obtain polyester-imide solution.Reaction solution is instilled in ethanol and obtain fibrous polyester-imide precipitation, dry, obtain polyester-imide powder.Wherein the second-order transition temperature of polymer powder is 217 DEG C.
By the polyester-imide powder N obtained, N-N,N-DIMETHYLACETAMIDE is configured to the solution that concentration expressed in percentage by weight is 10%, by casting method, its dissolution homogeneity is coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 DEG C and spends the night, then heat up according to follow procedure: 100 DEG C, 1 hour; 150 DEG C, 1 hour; 200 DEG C, 1 hour.Be down to after room temperature until temperature and take out sheet glass, be placed on demoulding in warm water, then film is placed in 100 DEG C of loft drier dryings and dewaters, obtain transparent polyester imide membrane, its thickness is 26 μm.
Detection data are as follows: FT-IR (film): 1780cm
-1(asymC=Ostretching), 1722cm
-1(symC=Ostretching), 1370cm
-1(C-Nstretching); The H103 resin of the film prepared by ultraviolet-visual spectrometer test aforesaid method, the UV cut-off wavelength of this film is 351nm, and the light transmission rate at 400nm place is 73%; The water-intake rate of film is 0.32%.
Comparative example 1
In this comparative example, transparent polyester imide resin material has following structural formula:
Concrete preparation process is identical with embodiment 1, adopt identical diamine monomer 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, just diester dianhydride is wherein replaced, trimellitic acid 1,2-anhydride Resorcinol ester is made into from terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester.
The second-order transition temperature of polyesterimide resin prepared by this comparative example is 220 DEG C, and the thickness of film is 20 μm, and its UV cut-off wavelength is 360nm; Light transmission rate at 400nm place is 50%; The water-intake rate of film is 0.58%.
Visible, adopt terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester is as the dianhydride monomer of polyester-imide, the properties of transparency of polyester-imide can be substantially increased, the light transmission rate at 400nm place has brought up to 73% from 50%, and the water-intake rate of film has also been reduced to 0.32% from original 0.58%.
Embodiment 2:
In the present embodiment, transparent polyester imide resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 2 of 1.3450g (4.0mmol); 2 '-bis-(trifluoromethyl)-4; 4 '-diaminodiphenyl oxide and 16 milliliters of N; N-N,N-DIMETHYLACETAMIDE adds in 50mL reaction flask; stirring at room temperature; treat 2; after 2 '-bis-(trifluoromethyl)-4，4′-diaminodipohenyl ether dissolves completely, then add the terephthalic acid two (3 of 1.8333g (4.0mmol); 4-dicarboxylic acid anhydride) phenyl ester; continuing stirring at room temperature 24 hours, the polyesteramide acid solution of obtained thickness, is then 10% by solution dilution to concentration expressed in percentage by weight.
Polyesteramide acid solution coating after this dilution be evenly coated on clean sheet glass, solution coating thickness is 0.5 millimeter, is positioned over by sheet glass in loft drier, heats up according to follow procedure: 80 DEG C, 1 hour; 150 DEG C, 1 hour; 260 DEG C, 1 hour.Be down to after room temperature until temperature and take out sheet glass, be placed on demoulding in water, then film is placed in 100 DEG C of loft drier dryings and dewaters, obtain transparent polyester imide membrane, its thickness is 20 μm.Wherein the second-order transition temperature of this film is 243 DEG C.
Detection data are as follows: FT-IR (film): 1776cm
-1(asymC=Ostretching), 1717cm
-1(symC=Ostretching), 1372cm
-1(C-Nstretching).The H103 resin of the film prepared by ultraviolet-visual spectrometer test aforesaid method, the UV cut-off wavelength of this film is 365nm, and the light transmission rate at 400nm place is 72%; The water-intake rate of film is 0.38%.
Embodiment 3
In the present embodiment, transparent polyester imide resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 4 of 2.2740 (4.0mmol); 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide and 16 milliliters of N; N-N,N-DIMETHYLACETAMIDE adds in 50mL reaction flask; stirring at room temperature; treat 4; after 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide dissolves completely; add the terephthalic acid two (3 of 1.8333g (4.0mmol) again; 4-dicarboxylic acid anhydride) phenyl ester; continuing stirring at room temperature 24 hours, the polyesteramide acid solution of obtained thickness, is then 10% by solution dilution to concentration expressed in percentage by weight.Then add the mixed solution of 4mL diacetyl oxide and 2mL pyridine, continue stirring at room temperature 24 hours, obtain polyester-imide solution.Reaction solution is instilled in ethanol and obtain fibrous polyester-imide precipitation, dry, obtain polyester-imide powder.Wherein the second-order transition temperature of polymer powder is 236 DEG C.
By the polyester-imide powder N obtained, N-N,N-DIMETHYLACETAMIDE is configured to the solution that concentration expressed in percentage by weight is 10%, by casting method, its dissolution homogeneity is coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 DEG C and spends the night, then heat up according to follow procedure: 100 DEG C, 1 hour; 150 DEG C, 1 hour; 200 DEG C, 1 hour.Be down to after room temperature until temperature and take out sheet glass, be placed on demoulding in warm water, then film is placed in 100 DEG C of loft drier dryings and dewaters, obtain transparent polyester imide membrane, its thickness is 22 μm.Wherein the second-order transition temperature of this film is 236 DEG C.
Detection data are as follows: FT-IR (film): 1783cm
-1(asymC=Ostretching), 1724cm
-1(symC=Ostretching), 1371cm
-1(C-Nstretching); The H103 resin of the film prepared by ultraviolet-visual spectrometer test aforesaid method, the UV cut-off wavelength of this film is 343nm, and the light transmission rate at 400nm place is 78%; The water-intake rate of film is 0.28%.
Claims (7)
1. a transparent polyester imide resin, is characterized in that, described transparent polyester imide resin has following structural formula:
Wherein, Ar is binary primary amine monomer residue, n be greater than 0 integer.
2. transparent polyester imide resin according to claim 1, is characterized in that, described Ar can be selected from following groups one or more:
3. transparent polyester imide resin according to claim 1 and 2, is characterized in that, the second-order transition temperature of described transparent polyester imide resin is 200 DEG C ~ 350 DEG C, and the light transmission rate at 400nm place is 70% ~ 90%, and water-intake rate is less than 0.5%.
4. a preparation method for the transparent polyester imide resin as described in any one of claims 1 to 3, is characterized in that, comprise the following steps: obtained by polycondensation by terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester and binary primary amine monomer;
The structural formula of terephthalic acid two (3,4-dicarboxylic acid anhydride) phenyl ester is as follows:
5. the preparation method of transparent polyester imide resin according to claim 4, is characterized in that, comprise the following steps:
(1) binary primary amine monomer is added in the polar aprotic solvent of nitrogen or protection of inert gas, stirring adds terephthalic acid two (3 after making it dissolve completely, 4-dicarboxylic acid anhydride) phenyl ester, stirring reaction 12 hours ~ 48 hours, obtains the polyesteramide acid solution of clear viscous;
(2) adopt hot imidization method or chemical imidization method that polyesteramide acid solution is prepared into polyester-imide solution, dry, obtained transparent polyester imide resin.
6. the preparation method of transparent polyester imide resin material according to claim 5, is characterized in that, described hot imidization method comprises: dry after polyesteramide acid solution being applied as film, obtained transparent polyester imide resin;
Described chemical imidization method comprises: the mixed solution adding diacetyl oxide and pyridine in polyesteramide acid solution, continue stirring reaction 12 hours ~ 48 hours, obtain polyester-imide solution, polyester-imide solution is poured in precipitation agent, fully washing, drying after collecting precipitation, obtained transparent polyester imide resin.
7. the preparation method of transparent polyester imide resin according to claim 4, is characterized in that, described binary primary amine monomer is selected from 3,3 '-diaminodiphenylsulfone(DDS), 4,4′ diaminodiphenyl sulfone, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,2 '-two (trifluoromethyl)-4，4′-diaminodipohenyl ether, two (4-aminophenyl) HFC-236fa of 2,2-, two (3-aminophenyl) HFC-236fa of 2,2-, two (3-amino-benzene oxygen) benzene of 1,3-, 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, two [4-(3-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-amino-2-4-trifluoromethylphenopendant) benzene of 1,3-, two (5-amino-3-4-trifluoromethylphenopendant) benzene of 1,3-, 4,4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 4,4 '-bis-(3-trifluoromethyl-5-amino-benzene oxygen) sulfobenzide, two [4-(2-trifluoromethyl-4-aminophenoxyl) phenyl] HFC-236fa of 2,2-, two [4-(3-trifluoromethyl-5-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, one or more in 3,3-bis-(4-aminophenyl)-3H-isobenzofuranone.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476912A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Composition is used in peeling layer formation |
| CN110183658A (en) * | 2018-02-22 | 2019-08-30 | 三星电子株式会社 | Polymer, the film including the polymer and the display equipment including the film |
| CN115386085A (en) * | 2022-09-21 | 2022-11-25 | 中国科学院宁波材料技术与工程研究所 | Polyester imide copolymer and preparation method and application thereof |
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| JP2007314443A (en) * | 2006-05-24 | 2007-12-06 | Manac Inc | Ester group-containing tetracarboxylic acid compound, polyesterimide precursror, polyesterimide, and method for producing them |
| CN102317352A (en) * | 2009-02-12 | 2012-01-11 | 本州化学工业株式会社 | Ester group-containing tetracarboxylic acid dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing same |
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2015
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| JP2007314443A (en) * | 2006-05-24 | 2007-12-06 | Manac Inc | Ester group-containing tetracarboxylic acid compound, polyesterimide precursror, polyesterimide, and method for producing them |
| CN102317352A (en) * | 2009-02-12 | 2012-01-11 | 本州化学工业株式会社 | Ester group-containing tetracarboxylic acid dianhydride, polyester polyimide precursor, polyesterimide, and methods for producing same |
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| MASATOSHI ET AL: "Poly(ester imide)s Possessing Low Coefficient of Thermal Expansion and Low Water Absorption", 《HIGH PERFORMANCE POLYMERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109476912A (en) * | 2016-08-03 | 2019-03-15 | 日产化学株式会社 | Composition is used in peeling layer formation |
| CN109476912B (en) * | 2016-08-03 | 2021-10-08 | 日产化学株式会社 | Composition for forming release layer |
| CN110183658A (en) * | 2018-02-22 | 2019-08-30 | 三星电子株式会社 | Polymer, the film including the polymer and the display equipment including the film |
| CN110183658B (en) * | 2018-02-22 | 2023-08-18 | 三星电子株式会社 | Polymer, film including the same, and display device including the film |
| CN115386085A (en) * | 2022-09-21 | 2022-11-25 | 中国科学院宁波材料技术与工程研究所 | Polyester imide copolymer and preparation method and application thereof |
| CN115386085B (en) * | 2022-09-21 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Polyester imide copolymer and preparation method and application thereof |
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