CN106939081A - 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 PDFInfo
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- CN106939081A CN106939081A CN201710307824.7A CN201710307824A CN106939081A CN 106939081 A CN106939081 A CN 106939081A CN 201710307824 A CN201710307824 A CN 201710307824A CN 106939081 A CN106939081 A CN 106939081A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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Abstract
The invention discloses a kind of side-chain polyimide material and its preparation method and application, construction unit A and construction unit B is included in the structural formula of the side-chain polyimide；Wherein, construction unit A is：Wherein, construction unit B is：
Description
Technical field
The present invention relates to a kind of side-chain polyimide material and its preparation method and application, belong to organic optical function material
Field.
Background technology
Electrooptical material is widely used in optic communication, the field such as optical oomputing.Practical electrooptical material is mainly inorganic crystalline substance at present
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, and is easy to modification, it is easy to processing and device,
Thus widely paid close attention to.
In order to reach the standard of practicality, many organic polymers are used as the carrier of electric light molecule, wherein using the most
Extensive is exactly makrolon (APC), and to be electric light molecule can only be doped to makrolon the inside to its deficiency as object, lead
Cause the orientation stability of material bad, electro-optical activity decay is very fast.And polyimides has fabulous heat endurance, 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
Life-span.Meanwhile, using the chromophore molecule with higher second order susceptibility and high thermal stability, it is ensured that high electro-optical activity it is same
When ensure the stability of material, thus with more preferable practical prospect.
The content of the invention
An object of the present invention is to provide a kind of electro-optic polymer based on polyimide.
The second object of the present invention is to provide method simply, and mild condition is easy to precise control chromophore molecule content
Polyimide electro-optical material synthetic method.
The third object of the present invention is while ensureing that material possesses high electro-optical activity, with fabulous heat endurance, greatly
The service life of big lifting electrooptical material.
The technical scheme is that there is provided a kind of side-chain polyimide, the structural formula of the side-chain polyimide
In include construction unit A and construction unit B；
Wherein, construction unit A is：
Wherein, construction unit B is：
Wherein, construction unit A quantity is 1~1000, and construction unit B quantity is 1~1000 integer, and R represents hair
Color group, the structural formula of chromophore is：
Wherein, x is 2~6 integer, and y is 2~6 integer.
Further, construction unit A quantity is 2~800 integer, preferably 10~400 integer；Construction unit B
Quantity be 2~800 integer, preferably 10~400 integer.
The present invention further provides the preparation method of side-chain polyimide, comprises the following steps：
(1) by 3,3 ', 4,4 '-diphenyl ether tetraformic acid anhydride, double (3- amino-4-hydroxylphenyls) propane of 2,3- and 1,6- oneself
Diamines is dissolved in after organic solvent respectively mixes solution, and reaction adds dimethylbenzene after 24~48 hours, 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 for obtaining step (1) is dissolved in organic solvent, adds successively under inert gas shielding
Enter chromophore and catalyst, react 48-72 hours at room temperature, obtain mixed liquid B, side chain type is obtained after mixed liquid B is handled
Polyimides.
Further, in step (1), mixed liquor A is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, precipitation is separated out,
Filtering；Above-mentioned precipitation is dissolved in tetrahydrofuran again, then is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, precipitation, mistake is separated out
Filter；Obtain the polyimides of hydroxyl；In step (2), mixed liquid B is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, is analysed
Go out precipitation, filtering；Above-mentioned precipitation is dissolved in tetrahydrofuran again, then is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, is separated out
Precipitation, filtering；Finally obtain side-chain polyimide.
Further, in step (1), the molal quantity of 2,3- double (3- amino-4-hydroxylphenyls) propane and 1,6- hexamethylene diamine
Sum and 3,3 ', 4, the molal quantity of 4 '-diphenyl ether tetraformic acid anhydride is equal, wherein, 2,3- double (3- amino-4-hydroxylphenyls) propane
It is 1 with the ratio between the molal quantity of 1,6- hexamethylene diamines:0.5~1:3.
Further, the organic solvent in step (1) is DMF, DMA, diformazan
One or more in base sulfoxide, 1-METHYLPYRROLIDONE；Organic solvent in step (2) is tetrahydrofuran, dichloromethane, three
One or more in chloromethanes.
Further, in step (2), the catalyst is triphenylphosphine and azoethane dicarboxylic acid esters, and add
The molal quantity of triphenylphosphine and azoethane dicarboxylic acid esters is all higher 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 described side-chain polyimide is dissolved
Film, obtained film is placed in electric field afterwards, and using the method for corona polarizing, Kapton is polarized, obtained
Kapton with electro-optical activity.
Further, in the method for the corona polarizing, the voltage of electric field applied is 8000~15000V, polarization time
For 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 carried to side chain, and then the chromophore molecule with electro-optical activity is introduced on polymer lateral chain, is obtained
Side-chain polyimide electrooptical material.The polyimides is prepared into after film heating polarization in the electric field, prepares with high electricity
Photoactive Kapton, and considerably long stability can be kept under running conditions, can be electric as preparing
The material of optical device.
The method of the present invention is easy, and mild condition, while being easy to the precise control of Electro optic chromophore content, obtains high electric light
Living polymer, and keep good stability (to be placed 2000 hours at 85 DEG C of operating temperature, electro-optical activity remains to keep just
More than the 90% of initial value).
Following construction unit is included in the structure of the electro-optical activity polyimide material of the present invention：
Wherein：R is represented in a series of following chromophories, the molecular formula before the polyimides reaction of chromophore and hydroxyl
Carry hydroxyl：
Wherein：X=2~6, y=2~6.
The synthesis of the electro-optical activity polyimide material of the present invention：
(1) synthetic route of side chain type electric light polyimide material is as follows：
Wherein：R represents chromophore.
The synthetic method of the side chain type electric light polyimide material of the present invention comprises the following steps：
(1) by aromatic dianhydride 3,3 ', 4,4 '-diphenyl ether tetraformic of monomer acid anhydride (s-OPDA), hydroxy functional groups two
Double (3- amino-4-hydroxylphenyls) propane (BAP) of amine monomers 2,3- and aliphatic diamine monomers 1,6- hexamethylene diamines are dissolved in respectively
A certain amount of organic solvent.Above-mentioned dianhydride monomer is mixed with diamine monomer solution, reacted 24~48 hours under normal temperature.Then plus
Enter a certain amount of dimethylbenzene, be warming up to 150 DEG C of azeotropic band water, react 10~24 hours, be cooled to room temperature.Above-mentioned solution is slow
It is poured into the mixed solution of ethanol/water, and faintly acid is adjusted to watery hydrochloric acid, separates out precipitation, suction filtration.Will be above-mentioned after preliminarily dried
Precipitation 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 watery hydrochloric acid.Repeat
Precipitation, suction filtration process, finally obtain the polyimides of hydroxyl.
(2) polyimides for the hydroxyl for obtaining step (1) is dissolved in a certain amount of organic solvent, under nitrogen protection according to
Secondary addition chromophore molecule R and excessive catalyst.React 48-72 hours at room temperature, be slowly dropped into the mixing of ethanol/water
In solution, and faintly acid is adjusted to watery hydrochloric acid, separates out precipitation, suction filtration.After being dissolved with a small amount of solvent, repetition is settled out and suction filtration
Process repeatedly, obtains side chain type electric light polyimide material after vacuum drying, structure is shown in formula (I).
Organic solvent described in step (1) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl Asia
One kind in sulfone, 1-METHYLPYRROLIDONE.
Organic solvent described in step (2) is the one or more in tetrahydrofuran, dichloromethane, chloroform, excellent
Elect the mixed solution of tetrahydrofuran and dichloromethane, and tetrahydrofuran as：Dichloromethane 1:1.
Described 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.
The side chain type electro-optical activity polyimide material of the present invention is dissolved in a certain amount of organic solvent, can be applied using rotation
Embrane method carries out film, can obtain homogeneous, smooth Kapton.Obtained Kapton is placed in high voltage electric field
In, using the method for corona polarizing, Kapton is polarized, the polyimides with electro-optical activity can be obtained thin
Film.
Described organic solvent is selected from cyclopentanone, cyclohexanone, methylene bromide, 1,2- dichloroethanes and the chloroethenes of 1,1,2,2- tetra-
One kind in alkane.
Advantages of the present invention concentrates on the following aspects：
(1) applied to electrooptical material field, there is provided the polyimides with electro-optical activity by polyimides by the present invention
Synthetic method, reaction condition is gentle, and step is easy, is easy to precise 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 dichloromethane, 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 field such as optical oomputing.
(4) a series of polyimides for preparing of the present invention have it is very high answer electro-optical activity, and under running conditions can
Long-time retention property is stable, greatly promotes the service life of electrooptical material.
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
Double (3- amino-4-hydroxylphenyls) propane (5mmol) of body 2,3- and aliphatic diamine monomers 1,6- hexamethylene diamines (5mmol) are respectively
It is dissolved in DMAC N,N' dimethyl acetamide.Above-mentioned dianhydride monomer is mixed with diamine monomer solution, reacted 48 hours under normal temperature.Then plus
Enter 10mL dimethylbenzene, be warming up to 150 DEG C of azeotropic band water, react 24 hours, be cooled to room temperature.Above-mentioned solution is slowly poured into second
In the mixed solution of alcohol/water, and faintly acid is adjusted to watery hydrochloric acid, separates out precipitation, suction filtration.Above-mentioned precipitation is dissolved in after preliminarily dried
In a small amount of tetrahydrofuran, it is slowly dropped into the mixed solution of ethanol/water, and faintly acid is adjusted to watery hydrochloric acid.Repeat precipitation, suction filtration
Process repeatedly, is subsequently placed in 50 DEG C and is dried in vacuo 24 hours, obtain the polyimides PI-OH of hydroxyl.
Embodiment 2
Side chain type electro-optical activity polyimides PI-DR synthesis
The polyimides PI-OH (5mmol) that embodiment 1 is obtained is dissolved in the mixed of 30mL tetrahydrofurans and 20mL dichloromethane
Close in solution, then chromophore DR (1mmol), triphenylphosphine (1.2mmol), azoethane diformazan successively under nitrogen protection
Acid esters (1.2mmol).React 48 hours, be slowly dropped into the mixed solution of ethanol/water, and weak acid is adjusted to watery hydrochloric acid at room temperature
Property, separate out precipitation, suction filtration.After being dissolved with a small amount of tetrahydrofuran, repetition is settled out with suction filtration process repeatedly, after vacuum drying
To aubergine side chain type electric light polyimides PI-DR, wherein m=15, n=58.Tg:168℃；Td5%：295℃；UV-Vis (four
Hydrogen furans):λmax=470nm.
Embodiment 3
Side chain type electro-optical activity polyimides PI-TF synthesis
The polyimides PI-OH (5mmol) that embodiment 1 is obtained is dissolved in the mixed of 30mL tetrahydrofurans and 20mL dichloromethane
Close in solution, then chromophore TF (1.5mmol), triphenylphosphine (1.8mmol), azoethane two successively under nitrogen protection
Formic acid esters (1.8mmol).React 72 hours, be slowly dropped into the mixed solution of ethanol/water at room temperature, and be adjusted to watery hydrochloric acid weak
Acidity, separates out precipitation, suction filtration.After being dissolved with a small amount of tetrahydrofuran, repetition is settled out with suction filtration process repeatedly, after vacuum drying
Obtain aubergine side chain type electric light polyimides PI-TF.Tg:162℃；Td5%：280℃；UV-Vis (tetrahydrofuran):λmax=
550nm。
Embodiment 4
Side chain type electrooptics polyimides PI-DR synthesized in 0.20g embodiments 2 is added to 1.00mL cyclohexanone
In, stirring is completely dissolved to polymer for 3~12 hours.Then nanofiltration membrane is used, insoluble particles a small amount of among solution are removed,
Spin-coating method film is used on ito glass substrate.It is 800~1200 revs/min, vacuum of the obtained film at 60 DEG C to control rotating speed
Dried 24 hours in drying box.Film thickness is between 2~4 μm.Then obtained electro-optical activity polyimides PI-DR films are used
Corona polarizing, poling temperature is between 150 DEG C~170 DEG C, and the polarization time is 5~15 minutes, polarizing voltage control 8000~
The distance between 15000V or so, needle point and thin polymer film are 1 centimetre；Electro-optic coefficient (r33) pass through the method for the total reflection that decays
Determine, the maximum electro-optic coefficient measured is 26.6pm/V.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 embodiments 3 according to the same step of embodiment 4,
Electric light polyimides PI-TF films are made.The maximum electro-optic coefficient measured after corona polarizing is used for 56.8pm/V.At 85 DEG C
Place 2000 hours, electro-optic coefficient is maintained at the 92% of initial value.
Claims (10)
1. a kind of side-chain polyimide, it is characterised in that construction unit A is included in the structural formula of the side-chain polyimide
With construction unit B；
Wherein, construction unit A is：
Wherein, construction unit B is：
Wherein, construction unit A quantity is 1~1000, and construction unit B quantity is 1~1000 integer, and R represents chromophore,
The structural formula of chromophore is：
Wherein, x is 2~6 integer, and y is 2~6 integer.
2. side-chain polyimide as claimed in claim 1, it is characterised in that construction unit A quantity for 2~800 it is whole
Number, preferably 10~400 integer；Construction unit B quantity is 2~800 integer, preferably 10~400 integer.
3. the preparation method of side-chain polyimide described in a kind of claim 1 or 2, it is characterised in that comprise the following steps：
(1) by 3,3 ', 4,4 '-diphenyl ether tetraformic acid anhydride, double (3- amino-4-hydroxylphenyls) propane of 2,3- and 1,6- hexamethylene diamines
It is dissolved in respectively after organic solvent and mixes solution, reaction adds dimethylbenzene after 24~48 hours, is warming up to 145-155 DEG C, reaction
10~24 hours, room temperature is cooled to, mixed liquor A is obtained, the polyimides of hydroxyl is obtained after mixed liquor A is handled；
(2) polyimides for the hydroxyl for obtaining step (1) is dissolved in organic solvent, and hair is sequentially added under inert gas shielding
Color group and catalyst, react 48-72 hours, obtain mixed liquid B, side chain type polyamides is obtained after mixed liquid B is handled at room temperature
Imines.
4. preparation method as claimed in claim 3, it is characterised in that
In step (1), mixed liquor A is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, precipitation, filtering is separated out；Again will be above-mentioned
Precipitation is dissolved in tetrahydrofuran, then is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, separates out precipitation, filtering；Obtain hydroxyl
Polyimides；
In step (2), mixed liquid B is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, precipitation, filtering is separated out；Again will be above-mentioned
Precipitation is dissolved in tetrahydrofuran, then is poured into the aqueous solution of ethanol, and adjusts pH to 4-7, separates out precipitation, filtering；Finally obtain side
Chain polyimides.
5. preparation method as claimed in claim 1, it is characterised in that in step (1), 2,3- double (3- amino-4-hydroxy benzene
Base) propane and 1,6- hexamethylene diamine molal quantity sum and 3,3 ', 4, the molal quantity of 4 '-diphenyl ether tetraformic acid anhydride is equal, wherein, 2,
The ratio between molal quantity of double (3- amino-4-hydroxylphenyls) propane of 3- and 1,6- hexamethylene diamines is 1:0.5~1:3.
6. preparation method as claimed in claim 1, it is characterised in that the organic solvent in step (1) is N, N- dimethyl methyls
One or more in acid amides, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE；It is organic in step (2)
Solvent is the one or more in tetrahydrofuran, dichloromethane, chloroform.
7. synthetic method as claimed in claim 1, it is characterised in that in step (2), the catalyst is triphenylphosphine and two
Ethyl azodiformate, and the triphenylphosphine and the molal quantity of azoethane dicarboxylic acid esters that add are all higher than rubbing for chromophore
That number.
8. the preparation method described in claim 1 or 2, it is characterised in that chromophore：Triphenylphosphine：Azoethane dioctyl phthalate
The ratio between molal quantity of ester=1:1.2:1.2.
9. the application of side-chain polyimide described in a kind of claim 1 or 2, it is characterised in that by described side chain type polyamides
Film after imines dissolving, obtained film is placed in electric field, and using the method for corona polarizing, pole is carried out to Kapton
Change, obtain the Kapton with electro-optical activity.
10. application as claimed in claim 9, it is characterised in that in the method for the corona polarizing, the voltage of electric field applied
For 8000~15000V, the polarization time is 10~60 minutes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11267967B2 (en) | 2019-06-26 | 2022-03-08 | Samsung Electronics Co., Ltd. | Composition, electro-optic material, electro-optic device, and method for preparing electro-optic material |
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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 |
| US20100322586A1 (en) * | 2009-06-23 | 2010-12-23 | Nitto Denko Corporation | Polyimide compound, preparation method therefor, and optical film and optical waveguide produced by employing the compound |
| 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 |
-
2017
- 2017-05-04 CN CN201710307824.7A patent/CN106939081B/en active Active
Patent Citations (4)
| 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 |
| US20100322586A1 (en) * | 2009-06-23 | 2010-12-23 | Nitto Denko Corporation | Polyimide compound, preparation method therefor, and optical film and optical waveguide produced by employing the compound |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11267967B2 (en) | 2019-06-26 | 2022-03-08 | Samsung Electronics Co., Ltd. | Composition, electro-optic material, electro-optic device, and method for preparing electro-optic material |
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