CN104119531A - Diffluent transparent polyimide resin and preparation method thereof - Google Patents
Diffluent transparent polyimide resin and preparation method thereof Download PDFInfo
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- CN104119531A CN104119531A CN201410263703.3A CN201410263703A CN104119531A CN 104119531 A CN104119531 A CN 104119531A CN 201410263703 A CN201410263703 A CN 201410263703A CN 104119531 A CN104119531 A CN 104119531A
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Abstract
The invention discloses diffluent transparent polyimide resin. The diffluent transparent polyimide resin is obtained by carrying out condensation polymerization on 1,2-bis(3,4-dicarboxylic acid phenoxyl) cyclohexane dianhydride monomer and binary primary amine monomer. Phthalic anhydride structures at the two ends of a dianhydride monomer maintain high reaction activity of dianhydride, and an alicyclic structure with a middle twisted space structure has large free volume and steric hindrance and can effectively inhibit formation of a charge transfer complex in polyimide molecules and among polyimide molecules, so that transparency performance of the polyimide polymer is improved and a glass transition temperature is increased; a twisted 1,2-cyclohexane diol inner structure causes free volume of a molecular chain of polyimide to be increased, corresponding solubility property of transparent polyimide is improved, polyimide can be dissolved in common polar and nonpolar organic solvents at room temperature, and dissolution processability of polyimide resin is further improved. The invention also discloses a dianhydride monomer which can be used for preparing the diffluent transparent polyimide resin material.
Description
Technical field
The present invention relates to polyimide and preparation field thereof, be specifically related to a kind of diffluent clear polyimides resin and preparation method thereof.
Background technology
Polyimide is topmost kind in the aromatic heterocyclic copolymer growing up nearly half a century, also be the family macromolecule material that use temperature is the highest, there is the very excellent over-all propertieies such as physical strength is high, high temperature resistant, chemically stable, creep resistance, at aspects such as Aeronautics and Astronautics, electric, mechanical, microelectronics, chemical industry, be widely used.
The recent development along with new high-tech industry, the optical fields such as photoconduction, waveguide and liquid-crystal display are heat-resisting to height, the demand of the polyimide of high printing opacity is more and more urgent, because have the transparent polyimide of high thermal resistance and high light transmittance concurrently, can be applied to some other out of use fields of transparent resin, for example: 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 limited the further application of polyimide in photoelectric material, its major cause is to be present in the electron attraction of carbonyl in the dianhydride residue alternately occurring in main polymer chain and the molecule producing to electronic action of diamines residue and the formation of intermolecular charge transfer complex.Therefore can pass through to change molecular structure, exploitation can be used for flexible solar battery base plate, the flexible thermostable transparent polyimide resin material that shows or throw light on the fields such as base plate.
The method of the reduction polyimide color of taking at present mainly comprises:
(1) with dianhydride or the diamine monomer of whole fat structure, obtain the polyimide with fat units, fundamentally suppress the formation of charge transfer complex, but the dianhydride of lipid structure or diamines are due to the reduction of monomer reaction activity, or the generation of salt causes obtaining the polyimide of high molecular.As the Chinese invention patent application that the publication number Chinese invention patent that is CN101084254A and publication number are CN101831074A, CN1034707A has all been reported with the synthetic polyimide of alicyclic dianhydride monomer.
(2) in polyimide molecule structure, introduce containing fluoro substituents, because fluorine atom has very large electronegativity, can cut off the conjugation of electronic cloud, 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 with hexafluorodianhydride (6FDA), and referring to US Patent No. 4603061 and US4595548, but this dianhydride monomer is expensive.
(3) adopt with large side group or have the conjugation that unsymmetrical structure unit hinders electronic cloud, suppressing the formation of charge transfer complex, still this monomer is synthetic more difficult, cannot apply on a large scale.As reported a kind of polyimide of phenolic hydroxy group in the publication number Chinese invention patent application that is CN102516541A, this polyimide obtains by 3,3 '-diamino phenolphthalein and different diamines and dianhydride monomer polymerizations.
Publication number is in the Chinese invention patent application of CN102911359A, to have reported by 1,4-two (3,4-dicarboxylic acid phenoxy group) polyimide that hexanaphthene dianhydride and binary primary amine monomer are prepared by polycondensation, in molecular structure, introduced the structure of hexanaphthene, on the basis that does not reduce reactive behavior, improved the properties of transparency of polyimide, but other performance needs further to be improved as dissolved processing characteristics.
Summary of the invention
Technical purpose of the present invention is for above-mentioned prior art, and a kind of diffluent clear polyimides resin is provided, keeping on good optical transmittance and stable on heating basis, have an excellent solubility property.
The invention discloses a kind of diffluent clear polyimides resin material, described clear polyimides has following structural formula:
Wherein, Ar is binary primary amine monomer residue, and the quantity that n is repeating unit is to be greater than 0 integer.
Described Ar can be selected from one or more in following groups:
wherein, two horizontal lines "-" represent the connecting key of nitrogen-atoms in Ar group and repeating unit.
The second-order transition temperature of diffluent clear polyimides resin of the present invention can be 200 ℃～300 ℃, UV cut-off wavelength is 360nm～380nm, light transmission rate at 450nm place is 70%～90%, and can at room temperature be dissolved in conventional polarity and non-polar organic solvent (as N, N-N,N-DIMETHYLACETAMIDE, DMF, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), chloroform, tetrahydrofuran (THF) etc.).
In view of these performances, polyimide 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, has good dissolving processing characteristics simultaneously.
General more difficult film forming when the logarithmic viscosity number of polyimide of the present invention is less than 0.30dL/g, therefore, as the logarithmic viscosity number of polyimide is more preferably greater than equaling 0.30dL/g, generally more suitable at 0.35dL/g～1.00dL/g while adopting polyimide of the present invention to prepare film.
Polyimide logarithmic viscosity number testing method: polyimide powder or Kapton are dissolved in to N, in N-N,N-DIMETHYLACETAMIDE, obtaining concentration is the solution of 0.5g/dL (Grams Per Minute liter), by Ubbelohde viscometer, measure the logarithmic viscosity number of this solution 30 ℃ time, unit is dL/g.
The invention also discloses the preparation method of described diffluent clear polyimides resin, have easy and simple to handle, be easy to the advantages such as control.
The preparation method of described clear polyimides resin material, comprises step: by two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-and binary primary amine monomer, by polycondensation, obtained.
Described 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-are trans 1,2-two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride, cis 1, the mixture of any one in two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-or two kinds.Its corresponding structural formula is as follows:
Trans 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-
Cis 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-
The preparation method of described clear polyimides resin material comprises the steps:
By 1; 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and binary primary amine monomer are added in the phenol solvent of nitrogen or protection of inert gas; stirring adds catalyzer after it is dissolved completely; then reaction system is warming up to 180 ℃～210 ℃, reacts 6 hours～12 hours, after question response system is cooling, pour in precipitation agent; after collecting precipitation, fully wash, be dried, make clear polyimides resin.
Described phenol solvent can be selected one or more in meta-cresol, para-chlorophenol etc.
Described catalyzer can be selected isoquinoline 99.9.
Described precipitation agent can be selected ethanol.
Described rare gas element is selected the conventional rare gas element in this area, as argon gas etc.
Described 1, the mol ratio of two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-and binary primary amine monomer is 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 '-bis-(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.
The invention also discloses a kind of dianhydride monomer, is trans 1, two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and/or the cis 1 of 2-, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-; Can be used for preparing described diffluent clear polyimides resin.
In the design of dianhydride, continue the structure that employing alicyclic ring and phthalic anhydride combine, introducing on the basis of alicyclic ring raising properties of transparency, continue to retain the high reaction activity of aromatic dianhydride.On the basis of while disclosed dianhydride monomer in the patent documentation that publication number was CN102911359A originally, by improving spatial warping and the asymmetry of dianhydride, thereby reach the conjugation that hinders electronic cloud, suppress the formation of charge transfer complex, improve the properties of transparency of polyimide, 1 of distortion simultaneously, 2-cyclohexane diol structure has increased intermolecular free volume, improves the corresponding solubility property of clear polyimides.
Wherein, trans 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-, cis 1, the structural formula of two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-is as follows:
Trans 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-
Cis 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-
The invention also discloses the preparation method of described dianhydride monomer, adopting 1,2-cyclohexane diol and 4-nitro-phthalonitrile is raw material, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydride monomers of preparation 1,2-.
The preparation method of described dianhydride monomer comprises:
(1), under the effect of sodium hydride, 1,2-cyclohexane diol is reacted after 8-24 hour with 4-nitrophthalonitrile, and reaction solution is poured into water, separate out precipitation, filter, obtain crude product, acetonitrile recrystallization, dry two (3, the 4-dinitrile phenoxy group) hexanaphthenes of 1,2-that obtain;
(2) two (3, the 4-dinitrile phenoxy group) hexanaphthenes of 1,2-are hydrolyzed in the ethanol of potassium hydroxide and water mixed solution, solid is separated out in acidifying, obtains two (3, the 4-diformyl phenoxy group) hexanaphthenes of 1,2-;
(3), by two (3,4-diformyl phenoxy group) the hexanaphthene diacetyl oxide recrystallizations of 1,2-, filtration drying, obtains two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-.
By to raw material 1, the control of 2-cyclohexane diol, can obtain 1 of isomorphism type not, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-:
When 1,2-cyclohexane diol is cis, what prepare is cis 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-;
Or, when 1,2-cyclohexane diol is while being trans, prepare for trans 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-;
Or, when 1,2-cyclohexane diol is when the back mixing compound, prepare for along back mixing, close 1, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-.
Compared with prior art, diffluent clear polyimides resin of the present invention adopts two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-to react and obtain polyimide with aromatic diamine.Due to the introducing of alicyclic structure hexanaphthene in dianhydride, suppressed charge transfer complex in polyimide molecule and intermolecular formation, improved properties of transparency.The reservation of two ends phthalic anhydride, makes dianhydride the same with common aromatic dianhydride monomer simultaneously, has very high reactive behavior, has overcome the low shortcoming of fatty dianhydride reactive behavior.Simultaneously with respect to former employing 1, 4-two (3, 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride reacts and obtains polyimide with aromatic diamine, owing to further improving the spatial warping effect of the intermediate ring hexane diol of dianhydride in the molecular designing of dianhydride, adopt 1, 2-cyclohexane diol is raw material, thereby make corresponding polyimide molecule there is larger free volume, effectively hindering the conjugation of electronic cloud, suppress the formation of charge transfer complex, when guaranteeing the properties of transparency of polyimide, 1 of distortion, the immanent structure of 2-cyclohexane diol increases by the molecular chain free volume of polyimide, improve the corresponding solubility property of clear polyimides, and then improved the dissolving processing characteristics of polyimide resin.
From reaction preparation, 1, 2-two (3, 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride monomer is with 1, 2-cyclohexane diol and 4-nitrophthalonitrile are raw material, with low cost, syntheti c route is ripe, dianhydride is very easy to obtain, and the polyimide resin material being obtained by this dianhydride is when keeping good properties of transparency and higher second-order transition temperature high, there is superior solubility, flexible substrate material at solar cell, flexible transparent conducting film substrate material, the association areas such as liquid crystal display material have good application prospect, there is good dissolving processing characteristics.
As novel polyimide resin material, its avatar comprises multiple, for example, polyimide resin material of the present invention can be made to film, plastics, fiber etc., is applied in various association areas.
Accompanying drawing explanation
Fig. 1 is the syntheti c route figure of two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-;
Fig. 2 is the example polymerization route map of preparation diffluent clear polyimides resin of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail.
Embodiment 1: trans 1, and the preparation of two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-:
Under nitrogen protection, in the three-necked bottle of 500mL, add 9.9g (60% solid content, mass percent, sodium hydride 248mmol), the N that adds again 100mL, dinethylformamide, after stirring at room 2 hours, then drip 1 of 11.5g (100mmol), the N of 2-trans cyclohexane glycol and 100mL, the mixed solution of dinethylformamide, after stirring at room 1 hour, under ice-water bath is cooling, add the 3-nitrophthalonitrile of 36.5g (210mmol) and the N of 100mL, the mixed solution of dinethylformamide, add rear stirred overnight at room temperature, reaction solution is poured into water, separate out precipitation, filter, wash with water, dry, obtain trans 1, 2-two (3, 4-dinitrile phenoxy group) the thick product of hexanaphthene.
By above-mentioned thick product recrystallization in 150mL acetonitrile solution, obtain trans 1, two (3,4-dinitrile phenoxy group) the hexanaphthene 19.5g of 2-, productive rate 53%, fusing point: 196 ℃.Detection data are as follows: detect data as follows: FT-IR (KBr, cm
-1): 3079,2947,2231,1596,1497,1384,1323,1261,1249,1093,1026,853cm
-1.
1h NMR (400MHz, DMSO-d
6, δ, ppm): 7.98 (d, J=8.8Hz, 2H), 7.81 (d, J=2.8Hz, 2H), 7.39 (dd, J
1=8.8Hz, J
2=2.8Hz, 2H), 4.82 (s, 2H), 2.22-2.07 (m, 1H), 1.78-1.64 (m, 1H), 1.56-1.39 (m, 2H).
7.3g (20mmol) is prepared as stated above 1,2-two (3,4-dinitrile phenoxy group) hexanaphthene reacts and refluxes four days in ethanol/water (60mL/60mL) mixed solution of the potassium hydroxide of 40.4g (720mmol), then with hcl acidifying, arrive pH=1, separate out a large amount of solids, filtration drying, obtains 1, two (3, the 4-dicarboxylic acid phenoxy group) hexanaphthenes of 2-.By trans 1 of gained, two (3, the 4-diformyl phenoxy group) hexanaphthenes of 2-110mL diacetyl oxide reflux 1 hour, filtered while hot, collect filtrate, after cooling, separate out white solid, filtration drying, obtains trans 1,2-two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride 4.1g, productive rate 50%, fusing point: 202 ℃.FT-IR(KBr,cm
-1):2956,1846,1772,1616,1594,1384,1290,1264,1077,1013,878,738cm
-1.
1H?NMR(400MHz,DMSO-d
6,δ,ppm):7.89(d,J＝8Hz,2H),7.69(d,J＝2Hz,2H),7.34(dd,J
1＝8Hz,J
2＝2Hz,2H),4.96(s,2H),2.23-2.08(m,1H),1.80-1.64(m,1H),1.62-1.44(m,2H).
What in following examples, adopt is trans 1, and 2-two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydrides are and prepare in embodiment 1.
The preparation of clear polyimides resin:
Embodiment 2:
In the present embodiment, diffluent clear polyimides resin has following structural formula:
Concrete preparation method is: under nitrogen protection; by 4 of 1.2971g (3.0mmol); trans 1 of 4 '-bis-(3-amino-benzene oxygen) sulfobenzide, 1.2504g (3.0mmol); 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and 10 milliliters of meta-cresols add in 50mL reaction flask; add again 3 isoquinoline 99.9; 195 ℃ of heated and stirred are reacted 8 hours; make the polyimide solution of thickness, when question response temperature drops to 60-80 ℃, with separating out after meta-cresol dilution in ethanol; after suction filtration; alcohol reflux boils washes 2 times, puts into oven drying, makes polyimide product.
The logarithmic viscosity number of polyimide product prepared by the present embodiment is 0.40dL/g, and second-order transition temperature is 205 ℃.
Polyimide powder N prepared by the present embodiment, it is 10% solution that N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with this solution of casting method, be evenly coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 ℃ and spends the night, then according to follow procedure, heat up: 150 ℃, 2 hours; 200 ℃, 1 hour.After temperature is down to room temperature, take out sheet glass, be placed on demoulding in water, then film is placed in to 100 ℃ of loft drier are dry to dewater, obtain transparent polyimide film, its thickness is 20 μ m.Detection data are as follows: FT-IR (film): 1776cm
-1(asym C=O stretching), 1718cm
-1(sym C=O stretching), 1369cm
-1(C-N stretching).The curve that sees through of testing film prepared by aforesaid method by ultraviolet-visual spectrometer, the UV cut-off wavelength of this film is 366nm, the light transmission rate at 450nm place is 81%.Solubility experiment the results are shown in Table 1.
Comparative example 1:
In this comparative example, clear polyimides resin has following structural formula:
Concrete preparation method is identical with embodiment 2, adopt identical diamine monomer 4,4 '-bis-(3-amino-benzene oxygen) sulfobenzide, just by wherein trans 1,2-two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride changes trans Isosorbide-5-Nitrae-bis-(3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride into.
The second-order transition temperature of polyimide resin prepared by this comparative example is 206 ℃, and the UV cut-off wavelength of film is 369nm, and the light transmission rate at 450nm place is 82%.Solubility experiment the results are shown in Table 1.
By comparative example, find, two kinds of clear polyimides do not have obvious difference on the basis of second-order transition temperature and visible light transmissivity, but on solubility property, trans 1, 2-two (3, 4-dicarboxylic acid phenoxy group) polyimide that prepared by hexanaphthene dianhydride has excellent solubility property, they can be at various conventional polarity (N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO)) and the lower room temperature of non-polar solvent (as chloroform and tetrahydrofuran (THF)) dissolve, and trans 1, 4-two (3, 4-dicarboxylic acid phenoxy group) polyimide that prepared by hexanaphthene dianhydride is at above-mentioned solvent (N, N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), chloroform) in, need heating for dissolving, some solvent (N, dinethylformamide, tetrahydrofuran (THF)) or even heating also can only be partly dissolved.
Embodiment 3:
In the present embodiment, clear polyimides resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 2 of 0.6723g (2.0mmol); 2 '-bis-(trifluoromethyl)-4; 1 of 4 '-diaminodiphenyl oxide, 0.8248g (2.0mmol); 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and 6 milliliters of meta-cresols add in 50mL reaction flask; add 3 isoquinoline 99.9,190 ℃ of heated and stirred are reacted 8 hours, make the polyimide solution of thickness again; when question response temperature drops to 60-80 ℃; with separating out in ethanol after meta-cresol dilution, after suction filtration, alcohol reflux boils washes 2 times; put into oven drying, make polyimide product.
The logarithmic viscosity number of polyimide resin prepared by the present embodiment is 0.47dL/g, and second-order transition temperature is 225 ℃.
Polyimide powder N prepared by the present embodiment, it is 10% solution that N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, with this solution of casting method, be evenly coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 ℃ and spends the night, then according to follow procedure, heat up: 150 ℃, 2 hours; 200 ℃, 1 hour.After temperature is down to room temperature, take out sheet glass, be placed on demoulding in water, then film is placed in to 100 ℃ of loft drier are dry to dewater, obtain transparent polyimide film, its thickness is 21 μ m.Detection data are as follows: FT-IR (film): 1778cm
-1(asym C=O stretching), 1721cm
-1(sym C=O stretching), 1376cm
-1(C-N stretching).The curve that sees through of testing film prepared by aforesaid method by ultraviolet-visual spectrometer, the UV cut-off wavelength of this film is 371nm, the light transmission rate at 450nm place is 78%.Solubility experiment the results are shown in Table 1.
Embodiment 4:
In the present embodiment, clear polyimides resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 4 of 1.1374g (2.0mmol); 1 of 4 '-bis-(2-trifluoromethyl-4-aminophenoxyl) sulfobenzide, 0.8335g (2.0mmol); 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and 8 milliliters of meta-cresols add in 50mL reaction flask; add again 3 isoquinoline 99.9; 205 ℃ of heated and stirred are reacted 8 hours; make the polyimide solution of thickness, when question response temperature drops to 60-80 ℃, with separating out after meta-cresol dilution in ethanol; after suction filtration; alcohol reflux boils washes 2 times, puts into oven drying, makes polyimide product.
The logarithmic viscosity number of polyimide resin prepared by the present embodiment is 0.67dL/g, and second-order transition temperature is 221 ℃.
Polyimide powder N prepared by embodiment, it is 10% solution that N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, by casting method, this solution is evenly coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 ℃ and spends the night, then according to follow procedure, heat up: 150 ℃, 2 hours; 200 ℃, 1 hour.After temperature is down to room temperature, take out sheet glass, be placed on demoulding in water, then film is placed in to 100 ℃ of loft drier are dry to dewater, obtain transparent polyimide film, its thickness is 20 μ m.Detection data are as follows: FT-IR (film): 1779cm
-1(asym C=O stretching), 1722cm
-1(sym C=O stretching), 1373cm
-1(C-N stretching).The curve that sees through of testing film prepared by aforesaid method by ultraviolet-visual spectrometer, the UV cut-off wavelength of this film is 366nm, the light transmission rate at 450nm place is 81%.Solubility experiment the results are shown in Table 1.
Embodiment 5:
In the present embodiment, clear polyimides resin material has following structural formula:
Concrete preparation method is: under nitrogen protection; by 1 of 0.9609g (3.0mmol); 1 of two (3-amino-benzene oxygen) benzene of 3-, 1.2251g (3.0mmol); 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and 9 milliliters of meta-cresols add in 50mL reaction flask; add again 3 isoquinoline 99.9; 185 ℃ of heated and stirred are reacted 12 hours; make the polyimide solution of thickness, when question response temperature drops to 60-80 ℃, with separating out after meta-cresol dilution in ethanol; after suction filtration; alcohol reflux boils washes 2 times, puts into oven drying, makes polyimide product.
The logarithmic viscosity number of polyimide resin prepared by the present embodiment is 0.40dL/g, and second-order transition temperature is 240 ℃.
Polyimide powder N prepared by the present embodiment, it is 10% solution that N-N,N-DIMETHYLACETAMIDE is configured to concentration expressed in percentage by weight, by casting method, this solution is evenly coated on clean sheet glass, solution coating thickness is 0.5 millimeter, sheet glass is positioned in the loft drier of 80 ℃ and spends the night, then according to follow procedure, heat up: 150 ℃, 2 hours; 200 ℃, 1 hour.After temperature is down to room temperature, take out sheet glass, be placed on demoulding in water, then film is placed in to 100 ℃ of loft drier are dry to dewater, obtain transparent polyimide film, its thickness is 20 μ m.Detection data are as follows: FT-IR (film): 1779cm
-1(asym C=O stretching), 1722cm
-1(sym C=O stretching), 1358cm
-1(C-N stretching).The curve that sees through of testing film prepared by aforesaid method by ultraviolet-visual spectrometer, the UV cut-off wavelength of this film is 370nm, the light transmission rate at 450nm place is 81%.Solubility experiment the results are shown in Table 1.
The solubility property test-results of the clear polyimides resin that table 1 is prepared respectively for embodiment 2-5 and comparative example in different solvents.Test condition: adopt the sample dissolution of 10mg in the solvent of 1mL, measure its solubility property.
Table 1
Note: " ++ " represents room temperature dissolving, and "+" represents heating for dissolving, "+-" represent that hot spots dissolves.
In the present invention, due to binary primary amine monomer and 1, 2-two (3, 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride is the amino and 1 by binary primary amine monomer while carrying out polycondensation, 2-two (3, 4-dicarboxylic acid phenoxy group) acid anhydrides of hexanaphthene dianhydride reacts, the skeleton structure of the binary primary amine monomer of arbitrary structures of the present invention all can not affect the carrying out of this polycondensation, therefore the binary primary amine monomer of arbitrary structures of the present invention all can synthesize the polyimide of counter structure according to the method described in the present invention, the Kapton of these structures all presents transparence, its second-order transition temperature is all at 200 ℃～300 ℃, UV cut-off wavelength is all at 360nm～380nm, at the light transmission rate at 450nm place all 70%～90%, .In preparation method of the present invention, the variation of parameter does not affect the preparation of polyimide, all can obtain the polyimide of structure of the present invention, so in preparation method of the present invention, the combination of arbitrary parameter all can realize the preparation of polyimide.Do not repeat them here.
Claims (8)
1. a diffluent clear polyimides resin, is characterized in that, described clear polyimides resin has following structural formula:
Wherein, Ar is binary primary amine monomer residue, and n is greater than 0 integer.
2. diffluent clear polyimides resin according to claim 1, is characterized in that, described Ar is one or more in following groups:
3. diffluent clear polyimides resin according to claim 1 and 2, is characterized in that, the second-order transition temperature of described clear polyimides resin is 200 ℃～300 ℃.
4. the preparation method of a diffluent clear polyimides resin according to claim 1, it is characterized in that, described preparation method comprises step: by two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-and binary primary amine monomer, by polycondensation, obtained.
5. the preparation method of diffluent clear polyimides resin according to claim 4, is characterized in that, is specially:
By 1; 2-two (3; 4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and binary primary amine monomer are added in the phenol solvent of nitrogen or protection of inert gas; stirring adds catalyzer after it is dissolved completely; then reaction system is warming up to 180 ℃～210 ℃, reacts 6 hours～12 hours, after question response system is cooling, pour in precipitation agent; after collecting precipitation, fully wash, be dried, make diffluent clear polyimides resin.
6. the preparation method of diffluent clear polyimides 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 '-bis-(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.
7. a dianhydride monomer, is characterized in that, described dianhydride monomer is trans 1, two (3,4-dicarboxylic acid phenoxy group) hexanaphthene dianhydride and/or the cis 1 of 2-, two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 2-.
8. a preparation method for dianhydride monomer according to claim 7, is characterized in that, described preparation method comprises:
(1), under the effect of sodium hydride, 1,2-cyclohexane diol is reacted after 8～24 hours with 4-nitrophthalonitrile, and reaction solution is poured into water, separate out precipitation, filter, obtain crude product, acetonitrile recrystallization, dry two (3, the 4-dinitrile phenoxy group) hexanaphthenes of 1,2-that obtain;
(2) two (3, the 4-dinitrile phenoxy group) hexanaphthenes of 1,2-are hydrolyzed in the ethanol of potassium hydroxide and water mixed solution, solid is separated out in acidifying, obtains two (3, the 4-diformyl phenoxy group) hexanaphthenes of 1,2-;
(3), by two (3,4-diformyl phenoxy group) the hexanaphthene diacetyl oxide recrystallizations of 1,2-, filtration drying, obtains two (3,4-dicarboxylic acid phenoxy group) the hexanaphthene dianhydrides of 1,2-.
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