CN107501552A - A kind of polyimides and its preparation method and application - Google Patents

Abstract

The invention belongs to polymeric material field, more particularly to a kind of polyimides and its preparation method and application.Polyimides provided by the invention includes the repeat unit with formula (I) structure：Formula (I)；In formula (I), R₁For one kind in having structure： R₂The residue after two amino is removed for diamine compound.Test result indicates that the transparent shape of polyimides provided by the invention, the UV cut-off wavelength of the polyimides is 291~320nm, and the optical transmittance at 450nm is 75~90%；There is good dissolubility in metacresol, N methyl pyrrolidones, N, N dimethyl acetamides etc., can partly be dissolved in chloroform etc.；Moreover, the glass transition temperature of the polyimides, all more than 200 DEG C, 5% thermal weight loss is more than 400 DEG C；Meanwhile its reduced inherent viscosity is more than 0.30dL/g, film forming is good.

Description

A kind of polyimides and its preparation method and application

It is on 01 07th, 2016 the applying date that the application, which is, Application No. 201610007792.4, and invention and created name is The divisional application of " a kind of polyimides and its preparation method and application ".

Technical field

The invention belongs to polymeric material field, more particularly to a kind of polyimides and its preparation method and application.

Background technology

In recent years, developing rapidly with photoelectric material, such as display, storage, waveguide and area of solar cell material Update, the part that tradition is processed or shaped by inorganic material has been difficult processing and the use demand for meeting user.Therefore, The flexible display material for can arbitrarily stretching, bend, folding and former state being returned to made by high molecular polymer by The photoelectric material of a new round is gradually led to change.

Polyimides (Polyimide, abbreviation PI) is a kind of high molecular polymer containing imide ring on main chain, due to It has good mechanical performance, resistance to elevated temperatures and radiation resistance, is widely used in the manufacture of flexible display material, but its There is also some problems during manufacture flexible display material, it is mainly shown as：1), the dissolubility of existing polyimide material It is poor, increase the production difficulty of flexible material；2), existing polyimide material is respectively provided with shallow or deep color, causes The optical transmittance of manufactured flexible material is relatively low.

Therefore, how improving the dissolubility of polyimides and improving its optical transmittance is problem urgently to be resolved hurrily at present.

The content of the invention

In view of this, it is an object of the invention to provide a kind of polyimides and its preparation method and application, the present invention carries The polyimides of confession has excellent optical transmittance and outstanding dissolubility.

The invention provides a kind of polyimides, including the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

Preferably, the R₂For one kind in having structure：

-(CH₂)_m-、

Wherein, 1≤m≤10.

Preferably, viscosity of the polyimides at 30 DEG C is 0.43~1.78dL/g.

Preferably, the repeat unit with formula (I) structure is specially formula (I-2), formula (I-4), formula (I-6), formula (I- 8) one kind in structure shown in~formula (I-20)：

The invention provides a kind of preparation method of polyimides, comprise the following steps：

Dianhydride compound and diamine compound carry out polycondensation reaction in the presence of a catalyst, obtain polyimides；

The dianhydride compound is 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride, 3,4,3 ', 4 '-dicyclohexyl ether tetramethyl Acid dianhydride, 2,3,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 1,4- are double (3,4- dicarboxyls oxocyclohexyl) cyclohexyl dianhydride, 2,5,7,10- decahydronaphthalenes tetracarboxylic acid dianhydride, 4,4 '-bis- decahydro naphthyl -1, 1 ', 8,8 '-tetracarboxylic acid dianhydride, two (3,4- dicarboxyls butylcyclohexyl) methane dianhydrides or 2,2- bis- (3,4- dicarboxyls butylcyclohexyl) hexafluoro Propane dianhydride；

The polyimides includes the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

Preferably, the diamine compound be 1,2- ethylenediamines, 1,3- propane diamine, Putriscine, 1,5- pentanediamines, 1, 6- butanediamine, m-phenylene diamine (MPD), p-phenylenediamine, 1,5- naphthylenediamines, 2,6- naphthylenediamines, 1,4- cyclohexanediamine, benzidine, 4,4 '-two Diaminodiphenylmethane, 4,4'- diaminodiphenyl ethers, 2,2- bis- (4- aminophenyls) propane, 4,4 '-diaminourea benzophenone, 4,4 '- Double (4- amino-benzene oxygens) benzene of diaminodiphenylsulfone, 1,3-, 1,4- double (4- amino-benzene oxygens) benzene, the hexamethylenes of 4,4 '-diaminourea two Double [4- (4- amino-benzene oxygens) phenyl] propane of methylmethane, 2,2-, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl or 4,4 '-bis- (4- Amino-benzene oxygen) diphenyl sulphone (DPS).

Preferably, the catalyst includes isoquinolin and/or benzoic acid.

Preferably, the dianhydride compound and the mol ratio of diamine compound are (0.8~1.2)：1.

Preferably, the temperature of the polycondensation reaction is 150~250 DEG C；The time of the polycondensation reaction is 12~20h.

The invention provides a kind of polyimides as described in above-mentioned technical proposal or above-mentioned technical proposal methods described system Thin polymer film made of the polyimides obtained.

Compared with prior art, the invention provides a kind of polyimides and its preparation method and application.The present invention provides Polyimides include with formula (I) structure repeat unit：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.Test result indicates that polyimides provided by the invention Transparent shape, the UV cut-off wavelength of the polyimides is 291~320nm, the optical transmittance at 450nm be 75~ 90%；There is good dissolubility in metacresol, 1-METHYLPYRROLIDONE, DMA etc., can partly be dissolved in Chloroform etc.；Moreover, the glass transition temperature of the polyimides, all more than 200 DEG C, 5% thermal weight loss is more than 400 DEG C；Together When, its reduced inherent viscosity is more than 0.30dL/g, and film forming is good.

Brief description of the drawings

In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis The accompanying drawing of offer obtains other accompanying drawings.

Fig. 1 is the dianhydride nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 1 provides；

Fig. 2 is the polymeric infrared light spectrogram that the embodiment of the present invention 2 provides；

Fig. 3 is the polymeric U visible absorption spectra figure that the embodiment of the present invention 2 provides；

Fig. 4 is the hot weightless picture for the polymer that the embodiment of the present invention 2 provides；

Fig. 5 is the dynamic thermomechanical analysis chart for the polymer that the embodiment of the present invention 2 provides；

Fig. 6 is the synthetic route chart for the 2,5,7,10- decahydronaphthalene tetracarboxylic acid dianhydrides that the embodiment of the present invention 5 provides；

Fig. 7 is the dianhydride nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 5 provides；

Fig. 8 is the dianhydride nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 6 provides；

Fig. 9 is the dianhydride nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 7 provides；

Figure 10 is the dianhydride nucleus magnetic hydrogen spectrum figure that the embodiment of the present invention 8 provides；

Figure 11 is the polymeric infrared light spectrogram that the embodiment of the present invention 9 provides；

Figure 12 is the polymeric U visible absorption spectra figure that the embodiment of the present invention 9 provides；

Figure 13 is the hot weightless picture for the polymer that the embodiment of the present invention 9 provides；

Figure 14 is the dynamic thermomechanical analysis chart for the polymer that the embodiment of the present invention 9 provides.

Embodiment

The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment Only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects Enclose.

In the present invention, involved structure is structural formula.

The invention provides a kind of polyimides, including the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

In one embodiment provided by the invention, the R₂For one kind in having structure：

-(CH₂)_m-、

Wherein, in-(CH₂)_m- in, m is the integer more than 0, in one embodiment provided by the invention, 1≤m≤10； In another embodiment provided by the invention, m=4,5,6,7 or 8.

In one embodiment provided by the invention, the repeat unit with formula (I) structure be specially formula (I-2), One kind in formula (I-4), formula (I-6), formula (I-8)~structure shown in formula (I-20)：

In one embodiment provided by the invention, the polyimides is made up of the repeat unit with formula (I) structure. In one embodiment provided by the invention, viscosity of the polyimides at 30 DEG C is 0.43~1.78dL/g；In this hair In another embodiment of bright offer, viscosity of the polyimides at 30 DEG C is 0.58~1.52dL/g.

Polyimides water white transparency provided by the invention, there is excellent optical transmittance, good heat resistance and outstanding Dissolubility, can have certain application in photoelectric fields such as flexible substrate material, liquid crystal display materials.Test result indicates that Polyimides good in optical property provided by the invention, glass transition temperature all more than 200 DEG C, 5% thermal weight loss 400 DEG C with On, described polyimides UV cut-off wavelength is 220~320nm, the optical transmittance at 450nm be 75~ 90%；There is good dissolubility in metacresol, 1-METHYLPYRROLIDONE, DMA etc., partly can be with molten In chloroform etc.；Meanwhile the reduced inherent viscosity of the polyimides is more than 0.30dL/g, film forming is good.

The invention provides a kind of preparation method of polyimides, comprise the following steps：

Dianhydride compound and diamine compound carry out polycondensation reaction in the presence of a catalyst, obtain polyimides；

The dianhydride compound is 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride, 3,4,3 ', 4 '-dicyclohexyl ether tetramethyl Acid dianhydride, 2,3,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 1,4- are double (3,4- dicarboxyls oxocyclohexyl) cyclohexyl dianhydride, 2,5,7,10- decahydronaphthalenes tetracarboxylic acid dianhydride, 4,4 '-bis- decahydro naphthyl -1, 1 ', 8,8 '-tetracarboxylic acid dianhydride, two (3,4- dicarboxyls butylcyclohexyl) methane dianhydrides or 2,2- bis- (3,4- dicarboxyls butylcyclohexyl) hexafluoro Propane dianhydride；

The polyimides includes the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

In preparation method provided by the invention, dianhydride compound and diamine compound is directly set to enter in the presence of a catalyst Row polycondensation reaction, you can obtain polyimides, the process is specially：

Dianhydride compound, diamine compound and catalyst are mixed in a solvent first.Wherein, the dianhydride compound is 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride, 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-two hexamethylenes Double (the 3,4- dicarboxyls oxocyclohexyl) rings of base ether tetracarboxylic acid dianhydride, 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 1,4- Hexyl dianhydride, 2,5,7,10- decahydronaphthalenes tetracarboxylic acid dianhydride, 4,4 '-bis- decahydro naphthyls -1,1 ', 8,8 '-tetracarboxylic acid dianhydride, two (3, 4- dicarboxyls butylcyclohexyl) methane dianhydride or 2,2- bis- (3,4- dicarboxyls butylcyclohexyl) hexafluoropropane dianhydride.

In the present invention, described 2,3, the structure of 2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride is as follows：

The structure of 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride is as follows：

The structure of 2,3,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride is as follows：

The structure of 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride is as follows：

The structure of double (3,4- dicarboxyls oxocyclohexyl) the cyclohexyl dianhydrides of the 1,4- is as follows：

The structure of the 2,5,7,10- decahydronaphthalenes tetracarboxylic acid dianhydride is as follows：

Described 4,4 '-bis- decahydro naphthyls -1,1 ', the structure of 8,8 '-tetracarboxylic acid dianhydride are as follows：

The structure of described two (3,4- dicarboxyls butylcyclohexyl) methane dianhydride is as follows：

The structure of 2,2- bis- (the 3,4- dicarboxyls butylcyclohexyl) hexafluoropropane dianhydride is as follows：

The source of the dianhydride compound is not particularly limited the present invention, can use commercial goods, can also use Method well known to those skilled in the art is prepared, and can also be prepared in accordance with the following methods：

Tetracid and acetic anhydride hybrid reaction, obtain the dianhydride compound.Wherein, the tetracid is having structure compound In one kind：

In the present invention, the source of the tetracid is not particularly limited, can prepared in accordance with the following methods：

Hydrogenate after four esters and alkali reacted in a solvent, be acidified with acid, obtain tetracid.Wherein, four esters of the hydrogenation are One kind in having structure：

In the present invention, the source of four esters of the hydrogenation is not particularly limited, can prepared in accordance with the following methods：

Four esters and hydrogen are reacted in a solvent in the presence of a catalyst, obtain hydrogenating four esters.Wherein, described four Ester is one kind in having structure：

In the present invention, the source of four ester is not particularly limited, and can prepare in accordance with the following methods：

Aromatic dianhydride is reacted in a solvent in the presence of a catalyst, obtains four esters.Wherein, the aromatic dianhydride For one kind in having structure：

In the present invention, aromatic dianhydride is carried out in course of reaction in a solvent in the presence of a catalyst, described to urge Agent is preferably BFEE；The amount ratio of the aromatic dianhydride and catalyst is preferably 200~300 (g)：220~ 250(mL).The solvent is preferably methanol；The amount ratio of the aromatic dianhydride and solvent is preferably 200~300 (g)：700 ~900 (mL).The mode of the reaction is preferably to be heated to reflux；The time of the reaction is preferably 8~9h.In the present invention, Reaction obtains the detailed processes of four esters and is the aromatic dianhydride in a solvent in the presence of a catalyst：Aromatic dianhydride is being catalyzed Reacted in a solvent in the presence of agent, obtain reaction solution；After reaction solution decompression steams catalysts and solvents, then carry out according to It is secondary to be recrystallized and washed, obtain four esters.

In the present invention, four ester can also be prepared in accordance with the following methods：

Aromatic dianhydride is reacted in a solvent with sodium carbonate first, obtains tetrasodium salt；The tetrasodium salt and sulphur afterwards Dimethyl phthalate reacts, and obtains four esters.The aromatic dianhydride and the mol ratio of sodium carbonate are preferably 1:(4~8), more preferably 1: 6；The temperature that the aromatic dianhydride is reacted with sodium carbonate is preferably room temperature；The aromatic dianhydride carries out anti-with sodium carbonate The time answered is preferably 6~12h, more preferably 10h；The aromatic dianhydride and the mol ratio of dimethyl suflfate are preferably 1：(8 ~12), more preferably 1:10；The tetrasodium salt and the temperature of dimethyl suflfate reaction are preferably 40~50 DEG C；The tetrasodium salt Time with dimethyl suflfate reaction is preferably 0.5~2h, more preferably 1h.In the present invention, the tetrasodium salt and sulfuric acid two The detailed process that methyl esters reacts to obtain four esters is：Tetrasodium salt reacts with dimethyl suflfate, obtains reaction solution；The reaction solution is successively Washed and recrystallized, obtain four esters.

In the present invention, four ester can also be prepared in accordance with the following methods：

Triphenylphosphine and 3- chloro O-phthalic esters are reacted in a solvent in the presence of a catalyst, obtain four esters.Its In, the mol ratio of triphenylphosphine and 3- chloro the O-phthalic ester is preferably 1：(5~9), more preferably 1:7.The catalysis Agent includes nickel chloride and/or nickelous bromide；The reducing agent is zinc powder；The mass ratio of the triphenylphosphine and catalyst is preferably (32~35)：(60~67).The solvent is preferably DMAC N,N' dimethyl acetamide；The amount ratio of the triphenylphosphine and solvent is excellent Elect as 32~35 (g)：260~300 (mL).The temperature of the reaction is preferably 60~80 DEG C；The time of the reaction is preferably 6 ~8h.In the present invention, triphenylphosphine in the presence of a catalyst and 3- the chloro O-phthalic ester is reacted in a solvent The detailed process for obtaining four esters is：First catalyst, triphenylphosphine and partial solvent are mixed at 50~60 DEG C, obtained dark brown Mixed liquor；Afterwards by the dark brown mixed liquor and 3- chloro O-phthalic esters and the solvent hybrid reaction of surplus, reacted Liquid；The reaction solution is filtered, washed and recrystallized successively, obtains four esters.

In the present invention, four ester can also be prepared in accordance with the following methods：

4- bromos naphthalene anhydride is reacted in a solvent with sodium carbonate first, obtains disodium salt；The disodium salt and sulphur afterwards Dimethyl phthalate reacts, and obtains diester.Wherein, the mol ratio of the 4- bromos naphthalene anhydride and sodium carbonate is preferably 1：(2~4), it is more excellent Elect 1 as:3；The temperature that the 4- bromos naphthalene anhydride is reacted with sodium carbonate is preferably room temperature；The 4- bromos naphthalene anhydride and sodium carbonate The time reacted is preferably 8~12h, more preferably 10h；The mol ratio of the 4- bromos naphthalene anhydride and dimethyl suflfate is preferred For 1：(3~7), more preferably 1:5；The disodium salt and the temperature of dimethyl suflfate reaction are preferably 40~50 DEG C；Described two Sodium salt and the time of dimethyl suflfate reaction are preferably 0.5~2h, more preferably 1h.In the present invention, the disodium salt and sulphur The detailed process that dimethyl phthalate reacts to obtain diester is：Disodium salt reacts with dimethyl suflfate, obtains reaction solution；The reaction solution Washed, recrystallized and vacuum sublimation successively, obtain diester.

After obtaining diester, triphenylphosphine and the diester are reacted in a solvent in the presence of a catalyst, obtain four esters. Wherein, the catalyst includes nickel chloride and/or nickelous bromide；The reducing agent is zinc powder；The solvent is preferably N, N- diformazans Yl acetamide；The mol ratio of the triphenylphosphine and diester is preferably 1：(2~4), more preferably 1:3；The temperature of the reaction Preferably 80~90 DEG C；The time of the reaction is preferably 2~3h.In the present invention, the triphenyl in the presence of a catalyst The detailed process that phosphine and diester are reacted to obtain in a solvent four esters is：First catalyst, triphenylphosphine and partial solvent are existed Mixed at 80~90 DEG C, obtain dark brown mixed liquor；Afterwards by the dark brown mixed liquor and the diester and the solvent of surplus Hybrid reaction, obtain reaction solution；The reaction solution is filtered, washed and recrystallized successively, obtains four esters.

In the present invention, it is described to urge during four esters and hydrogen are reacted in a solvent in the presence of a catalyst Agent is preferably rhodium/activated carbon；The mass ratio of four esters and catalyst is preferably 1：(0.1~0.3).The solvent is preferably Tetrahydrofuran (THF)；The amount ratio of four esters and solvent is preferably 5 (g)：40~60 (mL).The Hydrogen Vapor Pressure of the reaction Preferably 2~5MPa；The temperature of the reaction is preferably 120~140 DEG C；The time of the reaction is preferably 5~8h.In this hair In bright, the detailed process that four esters and hydrogen are reacted to obtain in a solvent four esters of hydrogenation in the presence of a catalyst is：Urging Four esters and hydrogen are reacted in a solvent in the presence of agent, obtain reaction solution；The reaction solution removes catalysts and solvents Afterwards, obtain hydrogenating four esters.

In the present invention, during four esters of the hydrogenation are acidified with acid after being reacted in a solvent with alkali, the alkali Preferably sodium hydroxide；The mol ratio of hydroxyl and four esters of hydrogenation is preferably (0.1~0.3) in the alkali：(0.01~0.02), More preferably 0.2：(0.012~0.013).The solvent is preferably methanol；The amount ratio of four esters of the hydrogenation and solvent is preferred For 5 (g)：25~30 (mL).The mode of the reaction is preferably to be heated to reflux；The time of the reaction is preferably 24~30h.Instead After should terminating, except solvent, obtain hydrogenating four ester alkaline hydrolysis products.Obtain after hydrogenating four ester alkaline hydrolysis products, the hydrogenation Four ester alkaline hydrolysis products are acidified with acid.Wherein, described be acidified with acid preferably uses 37wt% concentrated hydrochloric acids, it is described hydrogenation four esters with The mass ratio 5 of 37wt% concentrated hydrochloric acids：(50~60).The time being acidified with acid is preferably 1~2h.After acidifying terminates, obtain Tetracid.

In the present invention, during tetracid and the acetic anhydride hybrid reaction, the mol ratio of the tetracid and acetic anhydride Preferably (0.005~0.006)：(0.2~0.3), more preferably (0.0058~0.0059)：(0.23~0.24)；It is described anti- The mode answered is preferably to be heated to reflux；The time of the reaction is preferably 10~12h.In the present invention, the tetracid and acetic acid The detailed process that acid anhydride hybrid reaction obtains dianhydride compound is：Tetracid and the acetic anhydride hybrid reaction, obtains reaction solution；It is described Reaction solution is filtered, crystallized and dried successively, obtains the dianhydride compound.

In the present invention, it is described during the dianhydride compound, diamine compound and catalyst mix in a solvent Diamine compound be 1,2- ethylenediamines, 1,3- propane diamine, 1,4- butanediamine, 1,5- pentanediamines, 1,6- butanediamine, m-phenylene diamine (MPD), P-phenylenediamine, 1,5- naphthylenediamines, 2,6- naphthylenediamines, 1,4- cyclohexanediamine, benzidine, 4,4 '-MDA, 4,4'- Diaminodiphenyl ether, 2,2- bis- (4- aminophenyls) propane, 4,4 '-diaminourea benzophenone, 4,4 '-diaminodiphenylsulfone, 1,3- Double (4- amino-benzene oxygens) benzene of double (4- amino-benzene oxygens) benzene, 1,4-, 4,4 '-diamino-dicyclohexyl methane, the double [4- of 2,2- (4- amino-benzene oxygens) phenyl] propane, 4,4 '-bis- (4- amino-benzene oxygens) biphenyl or 4,4 '-bis- (4- amino-benzene oxygens) hexichol Sulfone.

In the present invention, the structure of 1, the 2- ethylenediamines is as follows：

The structure of the 1,3- propane diamine is as follows：

The structure of the 1,4- butanediamine is as follows：

The structure of the 1,5- pentanediamines is as follows：

The structure of the 1,6- butanediamine is as follows：

The structure of the m-phenylene diamine (MPD) is as follows：

The structure of the p-phenylenediamine is as follows：

The structure of the 1,5- naphthylenediamines is as follows：

The structure of the 2,6- naphthylenediamines is as follows：

The structure of the 1,4- cyclohexanediamine is as follows：

The structure of the benzidine is as follows：

The structure of the 4,4 '-MDA is as follows：

The structure of the 4,4'- diaminodiphenyl ethers is as follows：

The structure of 2,2- bis- (4- aminophenyls) propane is as follows：

The structure of 4,4 '-diaminourea benzophenone is as follows：

The structure of the 4,4 '-diaminodiphenylsulfone is as follows：

The structure of double (4- amino-benzene oxygens) benzene of the 1,3- is as follows：

The structure of double (4- amino-benzene oxygens) benzene of the 1,4- is as follows：

The structure of the 4,4 '-diamino-dicyclohexyl methane is as follows：

The structure of double [4- (4- amino-benzene oxygens) phenyl] propane of the 2,2- is as follows：

The structure of described 4,4 '-bis- (4- amino-benzene oxygens) biphenyl is as follows：

The structure of described 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s is as follows：

In the present invention, it is described during the dianhydride compound, diamine compound and catalyst mix in a solvent Catalyst is preferably isoquinolin and/or benzoic acid；The dianhydride compound and the mol ratio of catalyst preferably 1：(0.5~2), more Preferably 1:1.In one embodiment provided by the invention, the catalyst is isoquinolin and benzoic acid, the isoquinolin and The mol ratio of benzoic acid preferably 1：(0.5~2), more preferably 1:1.The solvent be preferably metacresol, phenol, parachlorophenol and One or more in sulfolane；The mass ratio of the dianhydride compound and solvent is preferably (0.5~1.2)：(4~9).At this In invention, the mol ratio of the dianhydride compound and diamine compound is preferably (0.8~1.2)：1, more preferably 1：1.Mixing After uniformly, mixed liquor is obtained.

After obtaining mixed liquor, the mixed liquor carries out polycondensation reaction.Wherein, the temperature of the polycondensation reaction is preferably 150 ~250 DEG C, more preferably 180~200 DEG C；The time of the polycondensation reaction is preferably 12~20h.At one provided by the invention In using isoquinolin and benzoic acid as the embodiment of catalyst, preferably first by the dianhydride compound, diamine compound and benzene first Acid carries out polycondensation reaction after mixing in a solvent, continues polycondensation reaction in addition isoquinolin afterwards.Wherein, first time polycondensation The time of reaction is preferably 2~8h, more preferably 5h；The time for continuing polycondensation reaction is preferably 12~18h, more preferably 15h. In the present invention, the polycondensation reaction is preferably carried out in protective gas atmosphere, the protective gas be preferably rare gas or Nitrogen.After reaction terminates, reaction solution is obtained.The reaction solution is post-processed, and obtains polyimides.In the present invention, it is described The process that reaction solution is post-processed is specially：With precipitant mix after reaction solution solubilization dilution agent, sediment is obtained；It is described heavy Starch is washed and dried successively, obtains polyimides.In the present invention, the precipitating reagent is preferably acetone, methanol and second One or more in alcohol；The detergent that the washing uses is preferably the one or more in methanol, ethanol and isopropanol.

The present invention has been synthesized with excellent using the dianhydride monomer and diamine monomer of specific structure as raw material using solution polycondensation Different optical transmittance and the polyimides of good heat resistance.Test result indicates that it is made using method provided by the invention The transparent shape of polyimides, for glass transition temperature all more than 200 DEG C, 5% thermal weight loss is described poly- more than 400 DEG C Acid imide UV cut-off wavelength is 220~320nm, and the optical transmittance at 450nm is 75~90%；Meanwhile this is poly- Imido reduced inherent viscosity is more than 0.30dL/g, and film forming is good.

Present invention also offers the side described in a kind of polyimides as described in above-mentioned technical proposal or above-mentioned technical proposal Thin polymer film made of polyimides made from method.

Thin polymer film provided by the invention is made up of the polyimides, and its specific preparation process is：

The polyimides is mixed with organic solvent first, obtains polyimide solution.Wherein, the polyimides is molten The solid content of polyimides is preferably 8~10wt% in liquid.Afterwards by the polyimide solution casting film-forming, polymer is obtained Film.

Thin polymer film provided by the invention has excellent optical transmittance and good heat resistance, in flexible liner ground The photoelectric fields such as material, liquid crystal display material have good application prospect.

For the sake of becoming apparent from, it is described in detail below by following examples.

Embodiment 1

The preparation of 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride：

(1) 69g zinc powders, 7.67g nickelous bromides, 32.21g triphenylphosphines are added to 132mlN, in N- dimethyl acetamides, To be stirred at 60 DEG C to dark brown, addition is dissolved in 132mlN, the 200g 3- chloro O-phthalic ester solutions of N- dimethyl acetamides, Maintain temperature to react 6h at 60~80 DEG C, filter off catalyst, watery hydrochloric acid is washed some times, and the esters of 143g tetra- are obtained with ethyl alcohol recrystallization.

(2) by the esters of 5g tetra- and 0.5g rhodiums/activated-carbon catalyst (Acros, Rhodium on activated carbon, 5%Rh) it is added in 250ml autoclaves, adds 40mlTHF, at 120 DEG C of temperature, Hydrogen Vapor Pressure 2~5Mpa magnetic agitations Reaction 5~8 hours, then filters out catalyst, then rotates out THF, four esters hydrogenated.

(3) obtained 5g is hydrogenated into four esters and is dissolved in 25ml methanol, added 40g 20wt% sodium hydroxide solutions, heat back Flowing, methanol is steamed after 24h, resulting solution is added in 56g concentrated hydrochloric acids and is acidified, and white solid is collected by filtration and obtains 2.3g tetracids, Filtrate is extracted with ether, then is rotated ether and obtained 1.5g tetracids.

(4) gained 2.5g tetracids are added in acetic anhydride, after being heated to reflux 10h, filtered while hot, make filtrate in refrigerator Stand cooling, depositing white crystal.Crystal is collected by filtration, lower dry 12h is vacuumized at 155 DEG C, obtains 1.03g dianhydrides.

To dianhydride obtained above carry out nucleus magnetic hydrogen spectrum (¹H NMR) characterize, as a result as shown in figure 1, Fig. 1 is of the invention real The dianhydride nucleus magnetic hydrogen spectrum figure of the offer of example 1 is provided.As seen in Figure 3, dianhydride produced by the present invention is 2,3,2 ', 3 '-two hexamethylenes Base tetracarboxylic acid dianhydride.

Embodiment 2

1) preparation of polyimides：

Under nitrogen protection, by 0.7276g 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride and 0.4756g4,4'- diaminourea Diphenyl ether and 0.2898g benzoic acid are added in polymerization bottle, add 4.81g metacresols, are heated to 90 DEG C and are stirred to completely molten Solution.180 DEG C of reaction 20h are warming up to after dissolving.Reaction terminate after, add metacresol dilution is cooled to 100 DEG C again, by solution contain into In ethanol, white stringy solids are obtained.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, gathered Acid imide.

Polyimides made from the present embodiment has following structure：

Infrared spectrum analysis is carried out to polyimides obtained above, as a result as shown in Fig. 2 Fig. 2 is the embodiment of the present invention 2 The polymeric infrared light spectrogram of offer.

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.58dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, as a result as shown in figure 3, Fig. 3 is this hair The polymeric U visible absorption spectra figure that bright embodiment 2 provides.As seen in Figure 3, polyamides made from the present embodiment is sub- Amine UV cut-off wavelength is 293nm, and the optical transmittance at 450nm is 81%.

Thermogravimetic analysis (TGA) (nitrogen atmosphere, 10 DEG C/min of heating rate, temperature range are carried out to polyimides obtained above 100~800 DEG C), as a result as shown in figure 4, Fig. 4 is the hot weightless picture for the polymer that the embodiment of the present invention 2 provides.Can by Fig. 4 To find out, 5% thermal weight loss of polyimides made from the present embodiment is 438 DEG C.

Dynamic thermomechanical analysis (frequency 1Hz, 3 DEG C/min of heating rate, temperature model are carried out to polyimides obtained above Enclose 50~350 DEG C), as a result as shown in figure 5, Fig. 5 is the dynamic thermomechanical analysis chart for the polymer that the embodiment of the present invention 2 provides. As seen in Figure 5, the glass transition temperature of polyimides made from the present embodiment is 297 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, N, N- dimethyl methyls Solvable at room temperature in acid amides, dimethyl sulfoxide (DMSO), chloroform, heating lower part is solvable in Isosorbide-5-Nitrae-dioxane, in tetrahydrofuran It is insoluble.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 3

1) preparation of polyimides：

Under nitrogen protection, by 0.6452g 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride and 0.4431g4,4 '-diaminourea Dicyclohexyl methyl hydride and 0.2570g benzoic acid are added in polymerization bottle, add 4.35g metacresols, are heated to 90 DEG C of stirrings extremely It is completely dissolved.180 DEG C of reaction 20h are warming up to after dissolving.After reaction terminates, add metacresol dilution and be cooled to 100 DEG C again, will be molten Liquid is contained in ethanol, obtains white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, Obtain polyimides.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.06dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 228nm, and the optical transmittance at 450nm is 86%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 2 Analysis, the results showed that, the glass transition temperature of the polyimides is 241 DEG C, and 5% thermal weight loss is 429 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable under heating, heating lower part is solvable in chloroform, insoluble in Isosorbide-5-Nitrae-dioxane, tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 4

1) preparation of polyimides：

Under nitrogen protection, by 1.0922g2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride and 0.4072g1,4- cyclohexanediamine It is added to 0.4350g benzoic acid in polymerization bottle, adds 6g metacresols, is heated to 90 DEG C of stirrings to being completely dissolved.After dissolving It is warming up to 180 DEG C of reaction 20h.After reaction terminates, add metacresol dilution and be cooled to 100 DEG C again, solution is contained in ethanol, obtained To white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, polyimides is obtained.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.76dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 238nm, and the optical transmittance at 450nm is 89%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 2 Analysis, the results showed that, the glass transition temperature of the polyimides is 301 DEG C, and 5% thermal weight loss is 428 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable under heating, heating lower part is solvable in chloroform, insoluble in Isosorbide-5-Nitrae-dioxane, tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 5

The preparation of 2,5,7,10- decahydronaphthalene tetracarboxylic acid dianhydrides：

2,5,7,10- decahydronaphthalene tetracarboxylic acid dianhydrides are prepared according to synthetic route shown in Fig. 6, Fig. 6 is that the embodiment of the present invention 5 carries The synthetic route chart of 2,5,7, the 10- decahydronaphthalene tetracarboxylic acid dianhydrides supplied, its specific preparation process are：

(1) 52.7g sodium carbonate is added in 700mL water, stirring is gradually added Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics to dissolving To dissolving, G4 sand core funnels filtering, filtrate is transferred in 2L there-necked flasks, and 62.5mL sulfuric acid is added at 40 DEG C by 50g, 70 DEG C of stirring 2d Dimethyl ester, 1h is stirred, add 52.7g sodium carbonate, after stirring 20min, add 95.4mL dimethyl suflfates, after stirring 1h, mistake Filter, solid are washed three times, drying, are recrystallized three times with Isosorbide-5-Nitrae-dioxane, are obtained pure white solid powder.

(2) by the esters of 4g tetra- and 1.2g rhodiums/activated-carbon catalyst (Acros, Rhodium on activated carbon, 5%Rh) it is added in 250mL autoclaves, adds 32mL THF, it is anti-at 120 DEG C of temperature, Hydrogen Vapor Pressure 5Mpa magnetic agitations Answer 8 hours, then filter out catalyst, then rotate out THF, four esters hydrogenated.

(3) 4g is hydrogenated into four esters and is dissolved in 20mL methanol, and add 34.8g 20wt% sodium hydroxide solutions, be heated to reflux, Methanol is steamed after 24h, continues resulting solution after reacting one day and is added to magnetic agitation 1h in 47.6g concentrated hydrochloric acids, solution ether Extraction, then ether is rotated, obtain 3.12g white tetracid solids.

(4) 1.5g tetracids are added in 18g acetic anhydrides, after being heated to backflow 9h, filter while hot, make filtrate in refrigerator Cooling is stood, separates out solid.Solid is collected by filtration, lower dry 12h is vacuumized at 155 DEG C, obtains dianhydride 0.45g.

To dianhydride obtained above carry out nucleus magnetic hydrogen spectrum (¹H NMR) characterize, as a result as shown in fig. 7, Fig. 7 is of the invention real The dianhydride nucleus magnetic hydrogen spectrum figure of the offer of example 5 is provided.As seen in Figure 7, dianhydride produced by the present invention is 2,5,7,10- decahydronaphthalenes four Formic acid dianhydride.

Embodiment 6

The preparation of 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride：

(1) under nitrogen atmosphere, by 100g 3,4,3 ', 4 '-diphenyl ether dianhydride, 500mL methanol and 160mL boron trifluoride second Ether is added in 1L there-necked flasks, mechanical agitation, is heated to 80 DEG C, reaction first takes 150~200mL out of after 8~9 hours with water knockout drum Methanol, is subsequently poured into water to stir and obtains blocks of solid for a moment, filters, vacuum drying at solid is washed three times, 50 DEG C Afterwards four ester powder of white are obtained with ethyl acetate and petroleum ether reprecipitation.

(2) by the esters of 5g tetra- and 0.5g rhodiums/activated-carbon catalyst (Acros, Rhodium on activated carbon, 5%Rh) it is added in 250mL autoclaves, adds 40mL THF, in 120 DEG C of temperature, Hydrogen Vapor Pressure 2~5Mpa magnetic agitation Lower reaction 5~8 hours, then filters out catalyst, then rotates out THF, four esters hydrogenated.

(3) 5g is hydrogenated into four esters and is dissolved in 25mL methanol, and add 40g20wt% sodium hydroxide solutions, be heated to reflux, 24h After steam methanol, resulting solution is added to magnetic agitation 1h, solution in 56g concentrated hydrochloric acids and extracted with ether, then rotates ether, obtains To 4.03g white tetracid solids.

(4) 2g tetracids are added in 24g acetic anhydrides, after being heated to backflow 10h, filter while hot, make filtrate in refrigerator Stand cooling, depositing white crystal.Crystal is collected by filtration, lower dry 12h is vacuumized at 155 DEG C, obtains 3,4,3 ', 4 '-two rings Hexyl ether tetracarboxylic acid dianhydride 0.78g.

To dianhydride obtained above carry out nucleus magnetic hydrogen spectrum (¹H NMR) characterize, as a result as shown in figure 8, Fig. 8 is of the invention real The dianhydride nucleus magnetic hydrogen spectrum figure of the offer of example 6 is provided.As seen in Figure 8, dianhydride produced by the present invention is 3,4,3 ', 4 '-two hexamethylenes Base ether tetracarboxylic acid dianhydride.

Embodiment 7

The preparation of 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride：

(1) under nitrogen atmosphere, by 90g2,3,2 ', 3 '-diphenyl ether dianhydride, 450mL methanol and 144mL BFEEs It is added in 1L there-necked flasks, mechanical agitation, is heated to 80 DEG C, reaction first takes 100~150mL first out of after 8~9 hours with water knockout drum Alcohol, is subsequently poured into water to stir and obtains blocks of solid for a moment, filters, at solid is washed three times, 60 DEG C after vacuum drying Four ester powder of white are obtained with ethyl acetate and petroleum ether reprecipitation.

(2) by the esters of 5g tetra- and 0.5g rhodiums/activated-carbon catalyst (Acros, Rhodium on activated carbon, 5%Rh) it is added in 250mL autoclaves, adds 40mL THF, in 120 DEG C of temperature, Hydrogen Vapor Pressure 2~5Mpa magnetic agitation Lower reaction 5~8 hours, then filters out catalyst, then rotates out THF, four esters hydrogenated.

(3) 5g is hydrogenated into four esters and is dissolved in 25mL methanol, and add 40g 20wt% sodium hydroxide solutions, be heated to reflux, 24h After steam methanol, resulting solution is added to magnetic agitation 1h, solution in 56g concentrated hydrochloric acids and extracted with ether, then rotates ether, obtains To 4.11g white tetracid solids.

(4) 2g tetracids are added in 24g acetic anhydrides, after being heated to backflow 10h, filter while hot, make filtrate in refrigerator Stand cooling, depositing white crystal.Crystal is collected by filtration, lower dry 12h is vacuumized at 155 DEG C, obtains 2,3,2 ', 3 '-two rings Hexyl ether tetracarboxylic acid dianhydride 0.91g.

To dianhydride obtained above carry out nucleus magnetic hydrogen spectrum (¹H NMR) characterize, as a result as shown in figure 9, Fig. 9 is of the invention real The dianhydride nucleus magnetic hydrogen spectrum figure of the offer of example 7 is provided.As seen in Figure 9, dianhydride produced by the present invention is 2,3,2 ', 3 '-two hexamethylenes Base ether tetracarboxylic acid dianhydride.

Embodiment 8

The preparation of 2,2- bis- (3,4- dicarboxyls butylcyclohexyl) hexafluoropropane dianhydride：

(1) under nitrogen atmosphere, by 110g 2,3,2 ', 3 '-diphenyl ether dianhydride, 255mL methanol and 100mL boron trifluoride second Ether is added in 500mL there-necked flasks, mechanical agitation, is heated to 80 DEG C, reaction is poured into water to stir after 8~9 hours and obtained for a moment To blocks of solid is obtained, filter, four ester powder of white are obtained with ethyl alcohol recrystallization after vacuum drying at solid is washed three times, 80 DEG C End.

(2) by the esters of 5g tetra- and 1g rhodiums/activated-carbon catalyst (Acros, Rhod ium on activated carbon, 5% Rh) it is added in 250mL autoclaves, adds 40mL THF, it is anti-at 120 DEG C of temperature, Hydrogen Vapor Pressure 2~5Mpa magnetic agitations Answer 5~8 hours, then filter out catalyst, then rotate out THF, four esters hydrogenated.

(3) 5g is hydrogenated into four esters and is dissolved in 25mL methanol, and add 40g 20wt% sodium hydroxide solutions, be heated to reflux, 24h After steam methanol, resulting solution is added to magnetic agitation 1h, solution in 56g concentrated hydrochloric acids and extracted with ether, then rotates ether, obtains To 3.86g white tetracid solids.

(4) 2g tetracids are added in 24g acetic anhydrides, after being heated to backflow 10h, filter while hot, make filtrate in refrigerator Stand cooling, depositing white crystal.Crystal is collected by filtration, lower dry 12h is vacuumized at 155 DEG C, obtains (3, the 4- dicarboxyls of 2,2- bis- Butylcyclohexyl) hexafluoropropane dianhydride 1.08g.

To dianhydride obtained above carry out nucleus magnetic hydrogen spectrum (¹H NMR) characterize, as a result as shown in Figure 10, Figure 10 is the present invention The dianhydride nucleus magnetic hydrogen spectrum figure that embodiment 8 provides.As seen in Figure 10, dianhydride produced by the present invention is 2,2- bis- (3,4- bis- Carboxycyclohexyl) hexafluoropropane dianhydride.

Embodiment 9

1) preparation of polyimides：

Specifically preparation method is：Under nitrogen protection, by the decahydronaphthalene tetracarboxylic acid dianhydrides of 0.3879g 2,5,7,10- and 0.2791g4,4'- diaminodiphenyl ether and 0.085g benzoic acid are added in polymerization bottle, are added 6.03g metacresols, are heated to 90 DEG C of stirrings are to being completely dissolved.180 DEG C of reaction 5h are warming up to after dissolving and add 0.09g isoquinolin, continues after reacting 15h, adds Metacresol dilution is cooled to 100 DEG C again, and solution is contained in ethanol, obtains white solid.Soxhlet extraction is carried out with ethanol.Extraction After complete, the lower 100 DEG C of drying of vacuum, polyimides is obtained.

Polyimides made from the present embodiment has following structure：

Infrared spectrum analysis is carried out to polyimides obtained above, as a result as shown in figure 11, Figure 11 is implementation of the present invention The polymeric infrared light spectrogram that example 9 provides.

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.74dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, as a result as shown in figure 12, Figure 12 is this The polymeric U visible absorption spectra figure that inventive embodiments 9 provide.As seen in Figure 12, polyamides made from the present embodiment Imines UV cut-off wavelength is 322nm, and the optical transmittance at 450nm is 83%.

Thermogravimetic analysis (TGA) (nitrogen atmosphere, 10 DEG C/min of heating rate, temperature range are carried out to polyimides obtained above 100~800 DEG C), as a result as shown in figure 13, Figure 13 is the hot weightless picture for the polymer that the embodiment of the present invention 9 provides.Pass through Figure 13 As can be seen that 5% thermal weight loss of polyimides made from the present embodiment is 479 DEG C.

Dynamic thermomechanical analysis (frequency 1Hz, 3 DEG C/min of heating rate) is carried out to polyimides obtained above, as a result As shown in figure 14, Figure 14 is the dynamic thermomechanical analysis chart for the polymer that the embodiment of the present invention 9 provides.It can be seen by Figure 14 Go out, the glass transition temperature of polyimides made from the present embodiment is 418 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) room It is solvable under temperature, it is insoluble in chloroform, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 10

1) preparation of polyimides：

Under nitrogen protection, by 0.5010g2,5,7,10- decahydronaphthalene tetracarboxylic acid dianhydrides and 0.5264g Isosorbide-5-Nitraes-bis- (4- amino Phenoxy group) benzene and 0.11g benzoic acid be added in polymerization bottle, adds 4.10g metacresols, 90 DEG C of stirrings are heated to completely molten Solution.180 DEG C of reaction 5h are warming up to after dissolving and add 0.12g isoquinolin, are continued after reacting 15h, metacresol dilution is added and cools again To 100 DEG C, solution is contained in ethanol, obtains white solid.Soxhlet extraction is carried out with ethanol.After having extracted, 100 under vacuum DEG C drying, obtain polyimides

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.77dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 330nm, and the optical transmittance at 450nm is 84%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 357 DEG C, and 5% thermal weight loss is 482 DEG C.

Above-mentioned gained polyimides is solvable at room temperature in metacresol, 1-METHYLPYRROLIDONE, DMA, It is solvable that lower part is heated in dimethyl sulfoxide (DMSO), it is insoluble in chloroform, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 11

1) preparation of polyimides：

Under nitrogen protection, by the decahydronaphthalene tetracarboxylic acid dianhydrides of 0.4942g 2,5,7,10- and 0.3736g 4,4 '-diaminourea two Cyclohexyl-methane and 0.11g benzoic acid are added in polymerization bottle, add 5.6g metacresols, are heated to 90 DEG C and are stirred to completely molten Solution.180 DEG C of reaction 5h are warming up to after dissolving and add 0.11g isoquinolin, are continued after reacting 15h, metacresol dilution is added and cools again To 100 DEG C, solution is contained in ethanol, obtains white solid.Soxhlet extraction is carried out with ethanol.After having extracted, 100 under vacuum DEG C drying, obtain polyimides

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.51dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 290nm, and the optical transmittance at 450nm is 85%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 312 DEG C, and 5% thermal weight loss is 461 DEG C.

Above-mentioned gained polyimides metacresol heating under it is solvable, 1-METHYLPYRROLIDONE, DMA, It is solvable that lower part is heated in dimethyl sulfoxide (DMSO), it is insoluble in chloroform, Isosorbide-5-Nitrae-dioxane and tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 12

1) preparation of polyimides：

Under nitrogen protection, by 0.6273g3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.3897g 4,4'- diamino Yl diphenyl ether and 0.119g benzoic acid are added in polymerization bottle, add 4.07g metacresols, are heated to 90 DEG C and are stirred to completely molten Solution.After 180 DEG C of reaction 20h are warming up to after dissolving, add metacresol dilution and be cooled to 100 DEG C again, solution is contained in ethanol, obtained To white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, polyimides is obtained.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.03dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 280nm, and the optical transmittance at 450nm is 87%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 285 DEG C, and 5% thermal weight loss is 437 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 13

1) preparation of polyimides：

Under nitrogen protection, by 0.7568g 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.6864g Isosorbide-5-Nitraes-bis- (4- amino-benzene oxygens) benzene and 0.143g benzoic acid are added in polymerization bottle, add 5.8g metacresols, are heated to 90 DEG C of stirrings To being completely dissolved.Be warming up to after dissolving 180 DEG C reaction 20h after, add metacresol dilution is cooled to 100 DEG C again, by solution contain into In ethanol, white stringy solids are obtained.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, gathered Acid imide.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：2.31dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 286nm, and the optical transmittance at 450nm is 86%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 235 DEG C, and 5% thermal weight loss is 442 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 14

1) preparation of polyimides：

Under nitrogen protection, by 0.8236g 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.5375g 4,4 '-two Amino bicyclic hexyl methane and 0.156g benzoic acid are added in polymerization bottle, add 5.8g metacresols, are heated to 90 DEG C of stirrings To being completely dissolved.Be warming up to after dissolving 180 DEG C reaction 20h after, add metacresol dilution is cooled to 100 DEG C again, by solution contain into In ethanol, white stringy solids are obtained.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, gathered Acid imide.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.32dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 225nm, and the optical transmittance at 450nm is 87%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 236 DEG C, and 5% thermal weight loss is 429 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable under heating, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 15

1) preparation of polyimides：

Under nitrogen protection, by 0.6213g 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.3860g 4,4'- bis- Amino-diphenylethers and 0.118g benzoic acid are added in polymerization bottle, add 4.04g metacresols, are heated to 90 DEG C and are stirred to complete Dissolving.After 180 DEG C of reaction 20h are warming up to after dissolving, add metacresol dilution and be cooled to 100 DEG C again, solution is contained in ethanol, Obtain white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, polyimides is obtained.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：0.96dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 282nm, and the optical transmittance at 450nm is 86%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 288 DEG C, and 5% thermal weight loss is 435 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 16

1) preparation of polyimides：

Under nitrogen protection, by 0.6723g 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.6098g Isosorbide-5-Nitraes-bis- (4- amino-benzene oxygens) benzene and 0.127g benzoic acid are added in polymerization bottle, add 5.12g metacresols, are heated to 90 DEG C of stirrings To being completely dissolved.Be warming up to after dissolving 180 DEG C reaction 20h after, add metacresol dilution is cooled to 100 DEG C again, by solution contain into In ethanol, white stringy solids are obtained.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, gathered Acid imide.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：2.01dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 287nm, and the optical transmittance at 450nm is 85%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 258 DEG C, and 5% thermal weight loss is 440 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 17

1) preparation of polyimides：

Under nitrogen protection, by 0.7536g 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride and 0.4918g4,4 '-diamino Base dicyclohexyl methyl hydride and 0.143g benzoic acid are added in polymerization bottle, add 5g metacresols, are heated to 90 DEG C and are stirred to complete Fully dissolved.After 180 DEG C of reaction 20h are warming up to after dissolving, add metacresol dilution and be cooled to 100 DEG C again, solution is contained into ethanol In, obtain white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, polyamides Asia is obtained Amine.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.32dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 227nm, and the optical transmittance at 450nm is 87%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 238 DEG C, and 5% thermal weight loss is 427 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable under heating, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 18

1) preparation of polyimides：

Under nitrogen protection, by 0.8273g2, (3, the 4- dicarboxyl butylcyclohexyl) hexafluoropropane dianhydrides of 2- bis- and 0.3630g4, 4'- diaminodiphenyl ethers and 0.111g benzoic acid are added in polymerization bottle, add 4.76g metacresols, are heated to 90 DEG C of stirrings To being completely dissolved.Be warming up to after dissolving 180 DEG C reaction 20h after, add metacresol dilution is cooled to 100 DEG C again, by solution contain into In ethanol, white stringy solids are obtained.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, gathered Acid imide.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.28dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 271nm, and the optical transmittance at 450nm is 88%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 307 DEG C, and 5% thermal weight loss is 461 DEG C.

Above-mentioned gained polyimides metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), Solvable at room temperature in chloroform, heating lower part is solvable in Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 19

1) preparation of polyimides：

Under nitrogen protection, by 0.8523g2, (3, the 4- dicarboxyl butylcyclohexyl) hexafluoropropane dianhydrides of 2- bis- and 0.5460g1,4- Double (4- amino-benzene oxygens) benzene and 0.114g benzoic acid are added in polymerization bottle, are added 5.6g metacresols, are heated to 90 DEG C and stir Mix to being completely dissolved.After 180 DEG C of reaction 20h are warming up to after dissolving, add metacresol dilution and be cooled to 100 DEG C again, solution is contained Enter in ethanol, obtain white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, obtain Polyimides.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：2.45dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 274nm, and the optical transmittance at 450nm is 87%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 295 DEG C, and 5% thermal weight loss is 465 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Embodiment 20

1) preparation of polyimides：

Under nitrogen protection, by 0.9458g2, (3, the 4- dicarboxyl butylcyclohexyl) hexafluoropropane dianhydrides of 2- bis- and 0.4360g4, 4 '-diamino-dicyclohexyl methane and 0.126g benzoic acid are added in polymerization bottle, are added 5.52g metacresols, are heated to 90 DEG C stirring is to being completely dissolved.After 180 DEG C of reaction 20h are warming up to after dissolving, add metacresol dilution and be cooled to 100 DEG C again, will be molten Liquid is contained in ethanol, obtains white stringy solids.Soxhlet extraction is carried out with ethanol.After having extracted, the lower 100 DEG C of drying of vacuum, Obtain polyimides.

Polyimides made from the present embodiment has following structure：

The viscosity of polyimides obtained above is tested at 30 DEG C, as a result for：1.48dL/g.

Ultraviolet-visible absorption spectroscopy analysis is carried out to polyimides obtained above, the results showed that, the polyimides is ultraviolet Absorption cutoff wavelength is 210nm, and the optical transmittance at 450nm is 91%.

Dynamic thermomechanical analysis and thermal weight loss point are carried out to polyimides obtained above using the test condition of embodiment 9 Analysis, the results showed that, the glass transition temperature of the polyimides is 262 DEG C, and 5% thermal weight loss is 439 DEG C.

Above-mentioned gained polyimides is in metacresol, 1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) Solvable at room temperature, heating lower part is solvable in chloroform, Isosorbide-5-Nitrae-dioxane, insoluble in tetrahydrofuran.

2) preparation of thin polymer film：

The polyimides of gained is configured to the solution that solid content is 10wt% with metacresol, sprawled using embrane method is scraped On the glass plate of cleaning.Glass plate is put into again and dried in film case, dries 8h at 80 DEG C.Then, glass plate is put into vacuum to dry In case, according to following steps temperature programming：100 DEG C/2h, 150 DEG C/2h, 200 DEG C/1h, 250 DEG C/1h.Treat that temperature is down to room temperature Afterwards, take out glass plate and be put into demoulding in water, you can obtain transparent polymer film.

Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

1. a kind of polyimides, including the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

2. polyimides according to claim 1, it is characterised in that the R₂For one kind in having structure：

-(CH₂)_m-、

Wherein, 1≤m≤10.

3. polyimides according to claim 1, it is characterised in that viscosity of the polyimides at 30 DEG C is 0.43 ~1.78dL/g.

4. polyimides according to claim 1, it is characterised in that the repeat unit with formula (I) structure is specific For one kind in formula (I-2), formula (I-4), formula (I-6), formula (I-8)~structure shown in formula (I-20)：

5. a kind of preparation method of polyimides, comprises the following steps：

Dianhydride compound and diamine compound carry out polycondensation reaction in the presence of a catalyst, obtain polyimides；

The dianhydride compound is 2,3,2 ', 3 '-dicyclohexyl tetracarboxylic acid dianhydride, 3,4,3 ', 4 '-dicyclohexyl ether tetracarboxylic acid two Acid anhydride, 2,3,3 ', the double (3,4- of 4 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 2,3,2 ', 3 '-dicyclohexyl ether tetracarboxylic acid dianhydride, 1,4- Dicarboxyl oxocyclohexyl) cyclohexyl dianhydride, 2,5,7,10- decahydronaphthalenes tetracarboxylic acid dianhydride, 4,4 '-bis- decahydro naphthyls -1,1 ', 8, 8 '-tetracarboxylic acid dianhydride, two (3,4- dicarboxyls butylcyclohexyl) methane dianhydrides or 2,2- bis- (3,4- dicarboxyls butylcyclohexyl) HFC-236fa Dianhydride；

The polyimides includes the repeat unit with formula (I) structure：

In formula (I), R₁For one kind in having structure：

R₂The residue after two amino is removed for diamine compound.

6. preparation method according to claim 5, it is characterised in that the diamine compound is 1,2- ethylenediamines, 1,3- Propane diamine, 1,4- butanediamine, 1,5- pentanediamines, 1,6- butanediamine, m-phenylene diamine (MPD), p-phenylenediamine, 1,5- naphthylenediamines, 2,6- naphthalenes two Amine, 1,4- cyclohexanediamine, benzidine, 4,4 '-MDA, 4,4'- diaminodiphenyl ethers, (the 4- aminobenzenes of 2,2- bis- Base) propane, 4,4 '-diaminourea benzophenone, 4,4 '-diaminodiphenylsulfone, double (4- amino-benzene oxygens) benzene of 1,3-, the double (4- of 1,4- Amino-benzene oxygen) benzene, 4,4 '-diamino-dicyclohexyl methane, double [4- (4- amino-benzene oxygens) phenyl] propane of 2,2-, 4,4 '- Double (4- amino-benzene oxygens) biphenyl or 4,4 '-bis- (4- amino-benzene oxygens) diphenyl sulphone (DPS)s.

7. preparation method according to claim 5, it is characterised in that the catalyst includes isoquinolin and/or benzoic acid.

8. preparation method according to claim 5, it is characterised in that mole of the dianhydride compound and diamine compound Than for (0.8~1.2)：1.

9. preparation method according to claim 5, it is characterised in that the temperature of the polycondensation reaction is 150~250 DEG C； The time of the polycondensation reaction is 12~20h.

10. a kind of any one of polyimides or claim 5~9 as described in any one of Claims 1 to 4 methods described is made Polyimides made of thin polymer film.