CN106939081B - A kind of side-chain polyimide material and its preparation method and application - Google Patents

A kind of side-chain polyimide material and its preparation method and application Download PDF

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CN106939081B
CN106939081B CN201710307824.7A CN201710307824A CN106939081B CN 106939081 B CN106939081 B CN 106939081B CN 201710307824 A CN201710307824 A CN 201710307824A CN 106939081 B CN106939081 B CN 106939081B
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structural unit
polyimides
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CN106939081A (en
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罗熙雯
王亮
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Aerospace Science and Industry Changsha New Materials Research Institute Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003Preparatory processes
    • C08G73/1007Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075Partially aromatic polyimides

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a kind of side-chain polyimide materials and its preparation method and application, include structural unit A and structural unit B in the structural formula of the side-chain polyimide;Wherein, structural unit A are as follows:Wherein, structural unit B are as follows:

Description

A kind of side-chain polyimide material and its preparation method and application
Technical field
The present invention relates to a kind of side-chain polyimide materials and its preparation method and application, belong to organic optical function material Field.
Background technique
Electrooptical material is widely used in optic communication, the fields such as optical oomputing.Electrooptical material practical at present is mainly inorganic crystalline substance Body, they have preferable physics and optical index.Relative to inorganic material, organic material has nonlinear factor big, accordingly Speed is fast, and laser damage threshold is high, and dielectric coefficient is low, with roomy, is readily synthesized, convenient for modification, easy to process and device, Thus widely paid close attention to.
In order to reach practical standard, many organic polymers are used as the carrier of electric light molecule, wherein using the most It is exactly widely polycarbonate (APC), and its deficiency is that electric light molecule can only be doped to inside polycarbonate as object, led Cause the orientation stability of material bad, electro-optical activity decaying is very fast.And polyimides has fabulous thermal stability, while side chain The structure of type can keep stability of the chromophore molecule in polymeric system for a long time, greatly promote the use of electrooptical material Service life.Meanwhile using the chromophore molecule with higher second order susceptibility and high thermal stability, guarantee the same of high electro-optical activity When ensure the stability of material, thus there is better practical prospect.
Summary of the invention
An object of the present invention is to provide a kind of electro-optic polymer based on polyimide.
It is simple that the second object of the present invention is to providing methods, mild condition, convenient for accurately controlling chromophore molecule content Polyimide electro-optical material synthetic method.
The third object of the present invention is that have fabulous thermal stability, greatly while guaranteeing that material has high electro-optical activity The big service life for promoting electrooptical material.
The technical scheme is that a kind of side-chain polyimide is provided, the structural formula of the side-chain polyimide In include structural unit A and structural unit B;
Wherein, structural unit A are as follows:
Wherein, structural unit B are as follows:
Wherein, the quantity of structural unit A is 1~1000, and the integer that the quantity of structural unit B is 1~1000, R represents hair Color group, the structural formula of chromophore are as follows:
Wherein, the integer that x is 2~6, the integer that y is 2~6.
Further, the integer that the quantity of structural unit A is 2~800, preferably 10~400 integer;Structural unit B Quantity be 2~800 integer, preferably 10~400 integer.
The present invention further provides the preparation method of side-chain polyimide, comprising the following steps:
(1) by bis- (3- amino-4-hydroxylphenyl) propane of 3,3 ', 4,4 '-diphenyl ether tetraformic acid anhydrides, 2,3- and 1,6- oneself Diamines mixes solution after being dissolved in organic solvent respectively, and dimethylbenzene is added after 24~48 hours in reaction, is warming up to 145-155 DEG C, Reaction 10~24 hours, is cooled to room temperature, obtains mixed liquor A, the polyimides of hydroxyl is obtained after mixed liquor A is handled;
(2) polyimides for the hydroxyl that step (1) obtains is dissolved in organic solvent, successively added under inert gas protection Enter chromophore and catalyst, reacts 48-72 hours at room temperature, obtain mixed liquid B, obtain side chain type after mixed liquid B is handled Polyimides.
Further, in step (1), mixed liquor A is poured into the aqueous solution of ethyl alcohol, and adjust pH to 4-7, precipitating is precipitated, Filtering;Above-mentioned precipitating is dissolved in tetrahydrofuran again, then is poured into the aqueous solution of ethyl alcohol, and adjusts pH to 4-7, precipitating, mistake is precipitated Filter;Obtain the polyimides of hydroxyl;In step (2), mixed liquid B is poured into the aqueous solution of ethyl alcohol, and adjusts pH to 4-7, is analysed It precipitates, filters out;Above-mentioned precipitating is dissolved in tetrahydrofuran again, then is poured into the aqueous solution of ethyl alcohol, and adjusts pH to 4-7, is precipitated Precipitating, filtering;Finally obtain side-chain polyimide.
Further, in step (1), 2,3- bis- (3- amino-4-hydroxylphenyl) propane and 1, the molal quantity of 6- hexamethylene diamine The sum of with 3,3 ', 4, the molal quantity of 4 '-diphenyl ether tetraformic acid anhydrides is equal, wherein 2,3- bis- (3- amino-4-hydroxylphenyl) propane It is 1:0.5~1:3 with the ratio between the molal quantity of 1,6- hexamethylene diamine.
Further, the organic solvent in step (1) is n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan One of base sulfoxide, N-Methyl pyrrolidone are a variety of;Organic solvent in step (2) is tetrahydrofuran, methylene chloride, three One of chloromethanes is a variety of.
Further, in step (2), the catalyst be triphenylphosphine and azoethane dicarboxylic acid esters, and be added The molal quantity of triphenylphosphine and azoethane dicarboxylic acid esters is all larger than the molal quantity of chromophore.
Further, chromophore: triphenylphosphine: the ratio between molal quantity of azoethane dicarboxylic acid esters=1:1.2:1.2.
The present invention further provides the application of the side-chain polyimide, and the side-chain polyimide is dissolved Obtained film is placed in electric field by film afterwards, using the method for corona polarizing, is polarized, is obtained to Kapton Kapton with electro-optical activity.
Further, in the method for the corona polarizing, the voltage of electric field applied is 8000~15000V, polarization time It is 10~60 minutes.
The present invention carries out ternary polymerization using aromatic dianhydride and aliphatic diamine and hydroxyl aromatic diamine, obtains The polyimides of hydroxyl is had to side chain, and then introduces the chromophore molecule with electro-optical activity on polymer lateral chain, is obtained Side-chain polyimide electrooptical material.The polyimides is prepared into after film heating polarization in the electric field, and preparing has high electricity Photoactive Kapton, and it is able to maintain quite long stability under running conditions, it can be used as preparation electricity The material of optical device.
Method of the invention is easy, mild condition, while being convenient for the accurate control of Electro optic chromophore content, obtains high electric light Living polymer, and good stability is kept (to place 2000 hours at 85 DEG C of operating temperature, electro-optical activity is still able to maintain just 90% or more of initial value).
Include following structural unit in the structure of electro-optical activity polyimide material of the invention:
Wherein: R represents a series of following chromophories, chromophore reacted with the polyimides of hydroxyl before molecular formula in Have hydroxyl:
Wherein: x=2~6, y=2~6.
The synthesis of electro-optical activity polyimide material of the invention:
(1) synthetic route of side chain type electric light polyimide material is as follows:
Wherein: R represents chromophore.
The synthetic method of side chain type electric light polyimide material of the invention the following steps are included:
(1) by aromatic dianhydride 3,3 ', 4,4 '-diphenyl ether tetraformic of monomer acid anhydride (s-OPDA), hydroxy functional groups two Bis- (3- amino-4-hydroxylphenyl) propane (BAP) of amine monomers 2,3- and aliphatic diamine monomers 1,6- hexamethylene diamine are dissolved in respectively A certain amount of organic solvent.Above-mentioned dianhydride monomer is mixed with diamine monomer solution, is reacted 24~48 hours under room temperature.Then plus Enter a certain amount of dimethylbenzene, is warming up to 150 DEG C of azeotropic band water, reacts 10~24 hours, be cooled to room temperature.Above-mentioned solution is slow It is poured into the mixed solution of ethanol/water, and is adjusted to faintly acid with dilute hydrochloric acid, precipitating is precipitated, filter.It will be above-mentioned after preliminarily dried Precipitating is dissolved in a small amount of tetrahydrofuran, is slowly dropped into the mixed solution of ethanol/water, and be adjusted to faintly acid with dilute hydrochloric acid.It repeats Precipitating filters process, finally obtains the polyimides of hydroxyl.
(2) polyimides for the hydroxyl that step (1) obtains is dissolved in a certain amount of organic solvent, under nitrogen protection according to Secondary addition chromophore molecule R and excessive catalyst.It reacts 48-72 hours at room temperature, is slowly dropped into the mixing of ethanol/water In solution, and it is adjusted to faintly acid with dilute hydrochloric acid, precipitating is precipitated, filters.After the dissolution of a small amount of solvent, repetition is settled out and is filtered Process is multiple, and side chain type electric light polyimide material is obtained after vacuum drying, and structure is shown in formula (I).
Organic solvent described in step (1) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl Asia One of sulfone, N-Methyl pyrrolidone.
Organic solvent described in step (2) is one of tetrahydrofuran, methylene chloride, chloroform or a variety of, excellent It is selected as the mixed solution of tetrahydrofuran and methylene chloride, and tetrahydrofuran: methylene chloride 1:1.
The catalyst is triphenylphosphine (P (Ph)3), azoethane dicarboxylic acid esters (DEAD), and ratio is preferably Chromophore molecule CHR:P (Ph)3: DEAD=1:1.2:1.2.
Side chain type electro-optical activity polyimide material of the invention is dissolved in a certain amount of organic solvent, and rotation can be used and apply Embrane method carries out film, and uniform, smooth Kapton can be obtained.Obtained Kapton is placed in high voltage electric field In, it using the method for corona polarizing, polarizes to Kapton, can obtain having the polyimides of electro-optical activity thin Film.
The organic solvent is selected from cyclopentanone, cyclohexanone, tetra- chloroethene of methylene bromide, 1,2- dichloroethanes and 1,1,2,2- One of alkane.
Advantages of the present invention concentrates on the following aspects:
(1) polyimides is applied to electrooptical material field by the present invention, provides the polyimides with electro-optical activity Synthetic method, reaction condition is mild, and step is easy, convenient for accurate control chromophore content.
(2) a series of electro-optical activity polyimides prepared by the present invention have good dissolubility, can preferably be dissolved in In common organic solvents, such as methylene chloride, tetrahydrofuran, cyclohexanone, cyclopentanone etc..
(3) a series of electro-optical activity polyimides prepared by the present invention have good film forming, can be used for electro-optical device Preparation, can be widely applied to optic communication, the fields such as optical oomputing.
(4) a series of polyimides prepared by the present invention answer electro-optical activity with very high, and under running conditions can Long-time retention property is stablized, and the service life of electrooptical material is greatly promoted.
Specific embodiment
Embodiment 1
The synthesis of the polyimides (PI-OH) of hydroxyl
By aromatic dianhydride 3,3 ', 4,4 '-diphenyl ether tetraformic of monomer acid anhydride (10mmol), the diamines list of hydroxy functional groups Bis- (3- amino-4-hydroxylphenyl) propane (5mmol) of body 2,3- and aliphatic diamine monomers 1,6- hexamethylene diamine (5mmol) are respectively It is dissolved in DMAC N,N' dimethyl acetamide.Above-mentioned dianhydride monomer is mixed with diamine monomer solution, is reacted 48 hours under room temperature.Then plus Enter 10mL dimethylbenzene, is warming up to 150 DEG C of azeotropic band water, reacts 24 hours, be cooled to room temperature.Above-mentioned solution is slowly poured into second In alcohol/water mixed solution, and it is adjusted to faintly acid with dilute hydrochloric acid, precipitating is precipitated, filters.Above-mentioned precipitating is dissolved in after preliminarily dried In a small amount of tetrahydrofuran, it is slowly dropped into the mixed solution of ethanol/water, and be adjusted to faintly acid with dilute hydrochloric acid.It repeats precipitating, filter Process is multiple, is subsequently placed in 50 DEG C and is dried in vacuo 24 hours, obtains the polyimides PI-OH of hydroxyl.
Embodiment 2
The synthesis of side chain type electro-optical activity polyimides PI-DR
The polyimides PI-OH (5mmol) that embodiment 1 obtains is dissolved in the mixed of 30mL tetrahydrofuran and 20mL methylene chloride It closes in solution, then successively chromophore DR (1mmol), triphenylphosphine (1.2mmol), azoethane diformazan under nitrogen protection Acid esters (1.2mmol).It reacts 48 hours, is slowly dropped into the mixed solution of ethanol/water, and be adjusted to weak acid with dilute hydrochloric acid at room temperature Property, precipitating is precipitated, filters.After the dissolution of a small amount of tetrahydrofuran, it is multiple that repetition settles out and filters process, must after vacuum drying To aubergine side chain type electric light polyimides PI-DR, wherein m=15, n=58.Tg:168℃;Td5%: 295 DEG C;UV-Vis (four Hydrogen furans): λmax=470nm.
Embodiment 3
The synthesis of side chain type electro-optical activity polyimides PI-TF
The polyimides PI-OH (5mmol) that embodiment 1 obtains is dissolved in the mixed of 30mL tetrahydrofuran and 20mL methylene chloride It closes in solution, then successively chromophore TF (1.5mmol), triphenylphosphine (1.8mmol), azoethane two under nitrogen protection Formic acid esters (1.8mmol).It reacts 72 hours, is slowly dropped into the mixed solution of ethanol/water at room temperature, and be adjusted to dilute hydrochloric acid weak Precipitating is precipitated in acidity, filters.After the dissolution of a small amount of tetrahydrofuran, it is multiple that repetition settles out and filter process, after vacuum drying Obtain aubergine side chain type electric light polyimides PI-TF.Tg:162℃;Td5%: 280 DEG C;UV-Vis (tetrahydrofuran): λmax= 550nm。
Embodiment 4
Side chain type electrooptics polyimides PI-DR synthesized in 0.20g embodiment 2 is added to 1.00mL cyclohexanone In, it is completely dissolved to polymer within stirring 3~12 hours.Then nanofiltration membrane is used, insoluble particles a small amount of in solution are removed, Spin-coating method film is used on ito glass substrate.Controlling revolving speed is 800~1200 revs/min, vacuum of the obtained film at 60 DEG C It is 24 hours dry in drying box.Film thickness is between 2~4 μm.Then obtained electro-optical activity polyimides PI-DR film is used Corona polarizing, for poling temperature between 150 DEG C~170 DEG C, the polarization time is 5~15 minutes, polarizing voltage control 8000~ 15000V or so, the distance between needle point and thin polymer film are 1 centimetre;Electro-optic coefficient (r33) pass through the method for decaying total reflection Measurement, the maximum electro-optic coefficient measured are 26.6pm/V.It is placed 2000 hours at 85 DEG C, electro-optic coefficient is maintained at initial value 95%.
Embodiment 5
By side chain type electric light polyimides PI-TF synthesized in 0.20g embodiment 3 step same according to embodiment 4, Electric light polyimides PI-TF film is made.Use the maximum electro-optic coefficient measured after corona polarizing for 56.8pm/V.At 85 DEG C It places 2000 hours, electro-optic coefficient is maintained at the 92% of initial value.

Claims (12)

1. a kind of side-chain polyimide, which is characterized in that include structural unit A in the structural formula of the side-chain polyimide With structural unit B;
Wherein, structural unit A are as follows:
Wherein, structural unit B are as follows:
Wherein, the quantity of structural unit A is 1~1000, and the integer that the quantity of structural unit B is 1~1000, R represents chromophore, The structural formula of chromophore are as follows:
Wherein, the integer that x is 2~6, the integer that y is 2~6.
2. side-chain polyimide as described in claim 1, which is characterized in that the quantity of structural unit A be 2~800 it is whole Number, the integer that the quantity of structural unit B is 2~800.
3. side-chain polyimide as described in claim 1, which is characterized in that the quantity of structural unit A be 10~400 it is whole Number.
4. side-chain polyimide as described in claim 1, which is characterized in that the quantity of structural unit B be 10~400 it is whole Number.
5. a kind of preparation method of any one of claim 1-4 side-chain polyimide, which is characterized in that including following step It is rapid:
(1) by bis- (3- amino-4-hydroxylphenyl) propane of 3,3 ', 4,4 '-diphenyl ether tetraformic acid anhydrides, 2,3- and 1,6- hexamethylene diamine Solution is mixed after being dissolved in organic solvent respectively, dimethylbenzene is added after 24~48 hours in reaction, is warming up to 145-155 DEG C, reaction It 10~24 hours, is cooled to room temperature, obtains mixed liquor A, the polyimides of hydroxyl is obtained after mixed liquor A is handled;
(2) polyimides for the hydroxyl that step (1) obtains is dissolved in organic solvent, sequentially adds hair under inert gas protection Color group and catalyst react 48-72 hours at room temperature, obtain mixed liquid B, side chain type polyamides is obtained after mixed liquid B is handled Imines.
6. preparation method as claimed in claim 5, which is characterized in that
In step (1), mixed liquor A is poured into the aqueous solution of ethyl alcohol, and adjusts pH to 4-7, precipitating, filtering is precipitated;It again will be above-mentioned Precipitating is dissolved in tetrahydrofuran, then is poured into the aqueous solution of ethyl alcohol, and adjust pH to 4-7, and precipitating, filtering is precipitated;Obtain hydroxyl Polyimides;
In step (2), mixed liquid B is poured into the aqueous solution of ethyl alcohol, and adjusts pH to 4-7, precipitating, filtering is precipitated;It again will be above-mentioned Precipitating is dissolved in tetrahydrofuran, then is poured into the aqueous solution of ethyl alcohol, and adjust pH to 4-7, and precipitating, filtering is precipitated;Finally obtain side Chain polyimides.
7. preparation method as claimed in claim 5, which is characterized in that in step (1), 2,3- bis- (3- amino-4-hydroxy benzene Base) propane and 1, the molal quantity of the sum of molal quantity of 6- hexamethylene diamine and 3,3 ', 4,4 '-diphenyl ether tetraformic acid anhydrides is equal, wherein and 2, The ratio between molal quantity of bis- (3- amino-4-hydroxylphenyl) propane of 3- and 1,6- hexamethylene diamine is 1:0.5~1:3.
8. preparation method as claimed in claim 5, which is characterized in that the organic solvent in step (1) is N, N- dimethyl methyl One of amide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N-Methyl pyrrolidone are a variety of;It is organic in step (2) Solvent is one of tetrahydrofuran, methylene chloride, chloroform or a variety of.
9. preparation method as claimed in claim 5, which is characterized in that in step (2), the catalyst is triphenylphosphine and two Ethyl azodiformate, and the molal quantity for the triphenylphosphine and azoethane dicarboxylic acid esters being added is all larger than rubbing for chromophore That number.
10. preparation method described in claim 5, which is characterized in that chromophore: triphenylphosphine: azoethane dicarboxylic acid esters The ratio between molal quantity=1:1.2:1.2.
11. a kind of application of side-chain polyimide as claimed in claim 1 or 2, which is characterized in that by the side chain type polyamides Film after imines dissolution, obtained film is placed in electric field, using the method for corona polarizing, carries out pole to Kapton Change, obtains the Kapton with electro-optical activity.
12. application as claimed in claim 11, which is characterized in that in the method for the corona polarizing, the electric field applied is electric Pressure is 8000~15000V, and the polarization time is 10~60 minutes.
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Publication number Priority date Publication date Assignee Title
CN1137044A (en) * 1996-05-10 1996-12-04 沈玉全 Process for preparing polyimide having side chain with azo-functional group
CN103289070A (en) * 2012-03-02 2013-09-11 中国科学院理化技术研究所 Second-order nonlinear optical polyarylester material, and synthetic method and application thereof
CN106543719A (en) * 2016-10-18 2017-03-29 中山大学 A kind of flexible light-transmitting polyimide film and its preparation method and application

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JP5210249B2 (en) * 2009-06-23 2013-06-12 日東電工株式会社 Polyimide compound and process for producing the same, and optical film and optical waveguide obtained from the compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1137044A (en) * 1996-05-10 1996-12-04 沈玉全 Process for preparing polyimide having side chain with azo-functional group
CN103289070A (en) * 2012-03-02 2013-09-11 中国科学院理化技术研究所 Second-order nonlinear optical polyarylester material, and synthetic method and application thereof
CN106543719A (en) * 2016-10-18 2017-03-29 中山大学 A kind of flexible light-transmitting polyimide film and its preparation method and application

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