CN110511229A - A kind of anhydride compounds and the preparation method and application thereof - Google Patents
A kind of anhydride compounds and the preparation method and application thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The present invention relates to technical field of polymer materials, especially transparent polyimide film technical field, and in particular to a kind of anhydride compounds and the preparation method and application thereof.Anhydride compounds of the present invention have distinctive alicyclic structure, can be indicated by any one in [chemical formula A] or [chemical formula B].It is polymerize with diamines to Kapton obtained realizes good optical characteristic to light transmittance >=85% that wavelength is 550mm light wave, overcome the saturate disadvantage of conventional fragrant adoption imide membrane, the application that may be implemented in transparent polyimide film field has been further equipped with the good prospect in flexible display apparatus or photoelectric field application.Preparation method provided by the present invention is stable, efficient, and raw material is easy to get, and preparation process is simple, convenient for the popularization of the anhydride compounds.
Description
Technical field
The present invention relates to technical field of polymer materials, especially transparent polyimide film technical field.Specifically,
It is related to a kind of anhydride compounds and the preparation method and application thereof.
Background technique
Polyimides (Polyimide, PI) refers to a kind of high polymer on main chain containing imide ring, by containing diamines and dianhydride
Compound be prepared through gradually polymerizeing.Because of distinctive imide ring, aromatic ring structure and its conjugation on PI main chain, make it
Have a characteristics such as excellent thermal stability, mechanical strength, dielectric properties and low thermal coefficient of expansion, thus in aerospace, micro-
The fields such as electronics, mechanical engineering, petrochemical industry, liquid crystal display are widely used.
With the development of photoelectric field, on the basis of keeping original good hot property and mechanical performance, to polyimides
Optical property more stringent requirements are proposed.And distinctive kinds of aromatic ring conjugation structure in traditional polyimide structures, result in molecule
Interior and Intermolecular charge transfer complex (CTC) formation, greatly affected the translucency of PI film, and show brown color
And poor light transmittance, PI film is limited in the development of photoelectric field.Meanwhile as intelligent electronic device in recent years is shown
Development of the device to bent direction opens high transparency PI film for the requirement for realizing this class of electronic devices Flexible Displays
Hair demand seems especially urgent.
To realize the good transparency of PI film, often need to redesign PI molecular structure.Such as it introduces and can break
The group (such as can realize curved ehter bond or sulfuryl) of planar conjugate structure or structure in bad main chain (such as spatial volume is big
Substituent group), introduce aliphatic structure (alicyclic ring or aliphatic structure) and containing fluorine structure etc., with destroy the conjugation effect of molecular structure with
Symmetry reduces intramolecular or intermolecular load transfer effect, to realize good transparence modified effect.It is often above-mentioned by selecting
One or more modes realize the raising of PI thin-film transparent.
In recent years, by using half ester ring type or full-cream ring type polyimides for not forming the mobile complex compound of charge theoretically
Technique study to make it show the transparency gradually increases, to prepare the transparent polyimides that can meet optoelectronic package requirement
The alicyclic structure of low electron density is introduced into polyimides main chain by film, people, prepares full-cream ring structure or half alicyclic ring (half
Fragrance) structure polyimides.Research finds the introducing of alicyclic structure due to inhibiting intramolecular and intermolecular charge transfer network
The formation for closing object, can significantly improve the transparency of Kapton, reduce coloring degree (A.S.Mathews etc. of film
.Macromol.Res., 2007,15,114-128).
Based on this, the present invention provides a kind of anhydride compounds, have with its distinctive full-cream ring or half alicyclic structure
While effect destroys the conjugated structure in PI membrane molecular structure, and weaken the charge transport capability in main structure;To realize
Good transparence modified effect, can be applied to transparent polyimide film field.
Summary of the invention
The first object of the present invention is to provide a kind of anhydride compounds, by following [chemical formula A] or [chemical formula
B] in any one expression:
[chemical formula A]
[chemical formula B]
In [the chemical formula A] and [chemical formula B], the XI、X2、X3、X4、X5、X6、X7、X8It is identical or different with n,
In, n=0-12 integer.
The XIIt is CmR1, S atom, N atom or O atom, m=0 or 1;
The X2It is CmR2, S atom, N atom or O atom, m=0 or 1;
The X3It is CmR3, S atom, N atom or O atom, m=0 or 1;
The X4It is CmR4, S atom, N atom or O atom, m=0 or 1;
The X5It is CmR5, S atom, N atom or O atom, m=0 or 1;
The X6It is CmR6, S atom, N atom or O atom, m=0 or 1;
The X7It is CmR7, S atom, N atom or O atom, m=0 or 1;
The X8It is CmR8, S atom, N atom or O atom, m=0 or 1.
The substituent R1To R10It is identical or different respectively, and be to be independently from each other hydrogen, heavy hydrogen, halogen, be substituted
Unsubstituted carbon atom number be 1 to 30 alkyl or alkoxy, substituted or unsubstituted carbon atom number be 2 to 30
Alkynyl that alkenyl, substituted or unsubstituted carbon atom number are 2 to 30, substituted or unsubstituted carbon atom number be 3 to
30 naphthenic base or cycloalkenyl, the aryl that substituted or unsubstituted carbon atom number is 6 to 30 or aryloxy group, be substituted or
The fragrant sulphur oxygen that alkane-sulfur oxyl that unsubstituted carbon atom number is 1 to 30, substituted or unsubstituted carbon atom number are 6 to 30
Alkylamino radical that base, substituted or unsubstituted carbon atom number are 1 to 30, substituted or unsubstituted carbon atom number be 6 to
30 aryl amine, substituted or unsubstituted and has miscellaneous original the aryl that substituted or unsubstituted carbon atom number is 6 to 50
Alkyl tin groups, alkyl silane groups that heteroaryl that the carbon atom number of sub- O, N or S are 2 to 50, carbon atom number are 1 to 24, carbon atom number be 6 to
24 aryl-silane base, substituted or unsubstituted boryl, substituted or unsubstituted phosphoryl, amino, sulfydryl, nitre
Any one in base, seleno, amide groups, ether and ester group.
The M is the aromatic ring that substituted or unsubstituted carbon atom number is 2 to 30 or heteroaromatic, 1,4- cyclohexadiene
Or the cyclohexadiene that hetero atom replaces.
Anhydride compounds provided by the invention are prepared it poly- because of its distinctive full-cream ring or half alicyclic structure
Good optical characteristics can be achieved in acid imide (polyimide, PI), and it is saturate to overcome conventional fragrant adoption imide membrane
Disadvantage.The application that may be implemented in transparent polyimide film field has been further equipped in Flexible Displays or photoelectric field application
Good prospect.
Further, the XI、X2、X3、X4、X5、X6、X7And X8It is identical or different, it is each independently selected from-CH-, S original
Son, N atom or O atom, n=0 or 1.When m is 0, the group of corresponding position is not present.The M is to substituted or unsubstituted
Phenyl ring or heteroaromatic, the heteroaromatic have hetero atom O, N or S.
The substituent group can be alkyl, alkoxy or aryl.The alkyl that the preferred carbon atom number of alkyl is 1~20,
The chain-like alkyl that further preferred carbon atom number is 1~6, the naphthenic base that carbon atom number is 3~8, it is further preferred that selection
The chain-like alkyl that carbon atom number is 1~4, the naphthenic base that carbon atom number is 5~7.As the example of alkyl, can specifically enumerate:
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, oneself
Base, 2- Methyl pentyl, 3- Methyl pentyl, 1,1,2- trimethyl-propyl, 3,3- dimethyl-butyl, heptyl, 2- heptyl, 3- heptan
Base, 2- methylhexyl, 3- methylhexyl, different heptyl, octyl, nonyl, decyl.
The carbon atom number of above-mentioned alkoxy is 1~16, preferably 1~3.Alkoxy is comprising unbranched alkoxy and with branch
Alkoxy.It as the example of alkoxy, can specifically enumerate: methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth oxygen
Base, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy, neopentyl oxygen, cyclopentyloxy, 2,
2- dimethyl propylene oxygroup, 1- ethylpropoxy, 1- methyl butoxy, 2- methyl butoxy, positive hexyloxy, dissident's oxygroup, 2- oneself
Oxygroup, 3- hexyloxy, 2- methyl amoxy, 3- methyl amoxy, 1,1,2- trimethyl propoxyl group, 3,3- dimethyl butyrate oxygroup,
Positive oxygroup in heptan, n-octyloxy, positive nonyl epoxide, n-decyloxy.
It as the example of aryl, can specifically enumerate: phenyl, naphthalene etc..
Further, the compound that chemical formula A is represented is selected from one of chemical formula A1~A18 or a variety of:
Further, the compound that chemical formula B is represented is selected from one of chemical formula B1~B19 or a variety of:
The second object of the present invention is to provide the preparation method of the anhydride compounds.
Wherein, the preparation method such as chemistry anhydride compounds shown in formula A the following steps are included:
(1) using compound A-1 as raw material, diamine compound A- is obtained by Mannich reaction (Mannich Reaction)
2;
(2) make compound A-2 that the reaction of deamination methyl occur, obtain bifunctional vinyl compound A-3;
(3) make compound A-3 that retaining ring occur with cyclopentadiene to react, obtain bicyclo hexene compound A-4;
(4) under palladium chtalyst, make compound A-4 that Infectious disease reaction occur, obtain compound A-5;
(5) make compound A-5 that hydrolysis and dehydration occur, obtain compound A-6.
The preparation methods of the anhydride compounds as shown in chemical formula B the following steps are included:
(1) using compound B-1 as raw material, diamine compound B-2 is obtained by Mannich reaction;
(2) make compound B-2 that the reaction of deamination methyl occur, obtain bifunctional vinyl compound B-3;
(3) make compound B-3 that retaining ring occur with cyclopentadiene to react, obtain bicyclo hexene compound B-4;
(4) under palladium chtalyst, make compound B-4 that Infectious disease reaction occur, obtain compound B-5;
(5) make compound B-5 that hydrolysis and dehydration occur, obtain compound B-6.
It in one embodiment of the invention, is to keep compound A-1 or B-1 and secondary amine salt and formaldehyde anti-in step (1)
It answers.The secondary amine salt is hydrochloride, sulfate or the acetate of secondary amine.The molar ratio of A-1 or B-1 and secondary amine salt is 1.0:2.0
~10.0;The molar ratio of A-1 or B-1 and formaldehyde is 1.0:2.0~10.0.
The reaction condition are as follows: reacted 0.5~10 hour under inert atmosphere, reaction temperature be 30~180 DEG C, preferably 85
~95 DEG C.
The reaction carries out in organic solvent, and the organic solvent is selected from tetrahydrofuran, methanol, ethyl alcohol, isopropanol, fourth
Alcohol, second eyeball, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, methylene chloride, a chlorine fluoroform
At least one of alkane, preferably isopropanol.
In one embodiment of the invention, in step (2) and (3), Mannich base and ring penta 2 are added in reaction process
Alkene;The molar ratio of the compound A-3 or B-3 and cyclopentadiene is 1.0:2.0~10.0.
The reaction condition are as follows: water-bath 0.5~10 hour under inert atmosphere, reaction temperature is 120~125 DEG C, excellent
It is selected as 85~95 DEG C.
In one embodiment of the invention, in step (4), under the action of palladium catalyst and copper catalyst, make to refine
It closes object and carbon monoxide is reacted with compound A-4 or B-4.
The mass ratio of the compound A-4 or B-4 and alcoholic compound is 1:1~100, preferably 1:5~50.The chemical combination
The molar ratio of object A-4 or B-4 and palladium catalyst is 1:0.001~1, preferably 1:0.01~0.5.The compound A-4 or B-4
Molar ratio with copper catalyst is 1:1.0~50, preferably 1:4.0~20.
The palladium catalyst used, is not particularly limited as long as comprising palladium.For example, palladium chloride, palladium bromide etc. can be enumerated
Halogenation palladium;The palladiums acylates such as acid chloride, oxalic acid palladium;The palladiums inorganic acid salt such as palladium nitrate, palladium sulfate;Palladium is set to be carried on carbon or oxidation
Palladium carbon or palladium aluminium oxide on the carriers such as aluminium etc. are, it is preferable to use palladium chloride or palladium carbon.
The alcoholic compound is not particularly limited, and can be selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, Zhong Ding
One of alcohol, the tert-butyl alcohol, amylalcohol, methyl cellosolve, ethoxy ethanol, ethylene glycol, triethylene glycol or more than one mixture;
It is preferred that one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol or more than one mixture;More preferable methanol, ethyl alcohol, isopropanol
One of or more than one mixture.
The copper catalyst is not particularly limited, and can be selected from monovalence copper oxide, monovalent copper chloride, monovalence copper bromide, two
One of valence copper oxide, divalent cupric chloride, divalent copper bromide or more than one mixture;It is preferred that divalent copper oxides, divalent
One of copper chloride, divalent copper bromide or more than one mixture;More preferably divalent cupric chloride.
It in one embodiment of the invention, is under the action of acid catalyst, by the compound A-5 in step (5)
Or B-5 is placed in heating stirring in organic solvent, brings it about dehydration.
The acid catalyst is not particularly limited, and can be inorganic acid, organic sulfonic acid, halogenated carboxylic acids, ion exchange resin
At least one of.The inorganic acid is selected from least one of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, sulfuric chlorohydrin, nitric acid, institute
It states organic sulfonic acid and is selected from least one of methanesulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, the halogenated carboxylic acids are selected from monoxone, three
At least one of fluoroacetic acid, the acid catalyst can also be ion exchange resin, sulfuric acid silica gel, zeolite, acidic alumina.
The organic solvent is not particularly limited, and can be organic acid solvent, be selected from toluene, dimethylbenzene, trimethylbenzene, benzene first
At least one of ether, diphenyl ether, methyltetrahydrofuran, hexamethylene, n-hexane, hexahydrotoluene, normal heptane, benzene, normal octane;
It is preferred that at least one of toluene, dimethylbenzene.
The heating temperature is 50~130 DEG C, preferably 80~120 DEG C.
The dosage of the organic solvent is suitably adjusted according to uniformity, the stirring property of reaction solution.The compound A-5 or
The mass ratio of B-5 and the organic solvent is 1:0.1~100, preferably 1:1~10.
The present invention illustrates the details of each reaction by embodiment.Those skilled in the art can change solvent, throw
Doses, reaction condition etc..In addition, respectively after reaction, such as filtering, extraction, distillation, distillation, recrystallization, column can be passed through
The common method such as chromatography carries out separation/purifying etc. of reaction product.
The raw material A -1, A-2 and B-1 can be closed by method known per se in public commercial source or document
At obtaining.For example, A1-1 is indone;A2-1 can refer to: Organic Process Research&Development, 21 (9),
1419-1422;The method prepared in 2017 is synthesized.B1-1 can refer to Angewandte Chemie, International
Edition,52(24),6277-6282;The method prepared in 2013 is synthesized.
Furthermore it is noted that part is not made used in each step being particularly limited in preparation method of the present invention
Solvent and its dosage, the separating-purifying of product, the rate of addition of reactant etc. are that those skilled in the art understand and grasp.
In the present invention, in addition to making special instruction, the volumetric usage of solvent is generally 5~15 times of reactant quality, specifically
Dosage can be according to the size appropriate adjustment of reaction substrate dosage and selected reaction flask;The rate of addition of reactant usually combines tool
Reaction speed comprehensively control of body etc..On the basis of disclosed by the invention, those skilled in the art can be corresponding according to the actual situation
Ground selects any available technical solution to realize the present invention.
Preparation method of the present invention can be stablized, be efficiently obtained anhydride compounds above-mentioned.
The third object of the present invention is to provide the anhydride compounds in the application in transparent polyimide film field.
Further, the anhydride compounds are used to prepare transparent polyimide film.
Transparent polyimide film of the present invention can be by the anhydride compounds, other aliphatic or aromatic series two
Amine compounds and diamine compound are prepared.
In one embodiment of the invention, the diamine compound is selected from 4,4 '-diaminodiphenyl ethers (ODA), right
Phenylenediamine (p-PDA), m-phenylene diamine (MPD) (m-PDA), o-phenylenediamine (o-PDA), 4,4 '-diaminodiphenylmethane (MDA), it is trans--
At least one of 1,4- cyclohexanediamine (t-DACH) and 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines) (TFMB).
Further, the transparent polyimide film is light transmittance >=85% of 550mm light wave to wavelength.It is described transparent
Kapton can be used for preparing flexible and transparent display base plate, optical transparent film, optical communication material and solar battery base
Plate.
Beneficial effects of the present invention:
(1) anhydride compounds provided by the invention can be used for transparent polyimide film field, distinctive full-cream with its
While ring or half alicyclic structure effectively destroy the conjugated structure in PI membrane molecular structure, and weaken the electricity in main structure
Lotus transfer ability, to realize good transparence modified effect.The transparent polyimide film is 550mm light wave to wavelength
Light transmittance >=85%.The application of transparent polyimide film is not particularly limited, flexible and transparent is can be applied to and shows
Substrate, the photoelectric fields such as optical transparent film, optical communication material and solar cell substrate.
(2) preparation method in the present invention can be stablized, be efficiently obtained anhydride compounds of the present invention, and former
Material is easy to get, and preparation process is simple, convenient for the popularization of the anhydride compounds.
Specific embodiment
Illustrate novel anhydride compounds of the present invention and preparation method thereof by the following examples.But this hair
It is bright to be not limited to following embodiment.The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..The original
Material unless otherwise instructed, can be obtained from public commercial source.
Anhydride compounds and preparation method thereof
The synthesis of compound A1
The synthetic line of prepare compound A1 is as follows:
Specific step is as follows:
(1) synthesis of compound A1-1
The aqueous dimethylamine 13.66g that mass fraction 50% is added into the three-necked flask of 250ml (contains dimethyl amine
151mmol).Aqueous hydrochloric acid solution (the containing hydrogen chloride of 19.11g mass fraction 30% is added into the dropping funel of 100ml
157.8mmol).Above-mentioned dropping funel is mounted on above-mentioned three-necked flask, is dripped above-mentioned aqueous hydrochloric acid solution under cold
Enter in above-mentioned aqueous dimethylamine, the hydrochloride of dimethyl amine is modulated in above-mentioned three-necked flask.Into above-mentioned three-necked flask
5.56g (185mmol) paraformaldehyde is added, the 2- indone of 8.38g (61.6.mmol) is then added.Nitrogen displacement is warming up to 85
~90 DEG C are reacted 3 hours, and reaction solution is obtained.And gas chromatographic analysis is carried out to reaction solution, the conversion ratio of confirmation 2- indone is
99%, the solution containing A1-1 is obtained, can directly be carried out in next step.
(2) synthesis of compound A1-3
Above-mentioned reaction solution is cooled to 50 DEG C, the dimethyl aqueous amine of methyl cellosolve (50ml) and mass fraction 50% is added
Solution 2.24g (containing dimethyl amine 24.8mmol) and cyclopentadiene 14.26g (containing cyclopentadiene 216mmol), obtains mixed liquor.
Nitrogen displacement is warming up to 115~120 DEG C, and reacts 1.5h at this temperature, is cooled to room temperature (25 DEG C) after reaction.So
Afterwards, above-mentioned mixed liquor is transferred in the separatory funnel of 500ml, is extracted with normal heptane (150ml), use normal heptane (80ml) again
Extraction, obtains normal heptane extracting solution after merging.The normal heptane extracting solution is successively used to the sodium hydrate aqueous solution of mass fraction 5%
(50ml) is washed 1 time, is washed 1 time with the aqueous hydrochloric acid solution (50ml) of mass fraction 5%.With the sodium bicarbonate of mass fraction 5%
Aqueous solution (50ml) washs 1 time, is washed 1 time with saturated salt solution (50ml).Extracting solution after washing is done with anhydrous magnesium sulfate
It is dry, anhydrous magnesium sulfate is then filtered out, is spin-dried for obtaining grease 17g, then carries out short-path distillation (125 DEG C, 11mmHg), is obtained
A1-3 12.6g.GC:98%, yield 71%.Cl-MS (m/z): 289.1514 (M+1).
(3) synthesis of compound A1-4
Methanol 364g, chloroform 62g, copper chloride (II) 136g (1011mmol), chlorine are added into the reaction vessel of capacity 1L
Change palladium 6g (33.7mmol), is stirred.After atmosphere gas in system is replaced into carbon monoxide, dissolved with dropwise addition in 3 hours
The solution of compound A1-3 in chloroform, wherein chloroform is 178g, and compound A1-3 is 19.402g (67.3mmol), 20
~25 DEG C react it 4 hours.Then, the atmosphere in system is replaced into argon gas from carbon monoxide, later from reaction mixture
In be distilled off solvent, add chloroform 621g.And then it is repeated twice same operation.Then obtained suspension is filtered to remove
Obtained solution is cleaned 3 times with saturated sodium bicarbonate aqueous solution 324g, and then is cleaned 3 times with pure water 324g by insoluble matter,
Backward organic layer in anhydrous magnesium sulfate 2.7g be added, active carbon 2.7g and be stirred.Then, subtracted after filtering solution
Pressure concentration, obtains white solid 51g.Then, by silica gel chromatography, (developing solvent is hexane: ethyl acetate=10: 1 (capacity
Than)) purified, obtain the A1-4 26.83g as white solid.Purity 99.1%, yield 76% based on HPLC analysis.
Cl-MS (m/z): 525.2046 (M+1).
(4) synthesis of compound A1
A1-4 6.23g (11.9mmol), formic acid 26.3g, p-methyl benzenesulfonic acid are put into the reaction vessel of capacity 100mL
Monohydrate 47mg (0.24mmol) reacts it 30 hours.After reaction, reaction solution is depressurized dense
Toluene 30g is added in contracting into concentrate.It is repeated 6 times the operation, formic acid is completely distilled off removing.Obtained suspension is filtered,
It after obtained solid is cleaned with toluene 30g, is dried in vacuo at 80 DEG C, obtains Off-white solid 4.7g.Later,
It is recrystallized using acetic anhydride, and then is recrystallized using n,N-dimethylacetamide, obtain the change as white solid
Close object A1 4.02g.Purity 98.3%, yield 79% based on 1H-MMR analysis.1Cl-MS (m/z): 433.12 (M+1).
The synthesis of compound A2
The synthetic line of prepare compound A2 is as follows:
Specific step is as follows:
(1) synthesis of compound A2-1
The aqueous dimethylamine 13.66g that mass fraction 50% is added into the three-necked flask of 250ml (contains dimethyl amine
151mmol).Aqueous hydrochloric acid solution (the containing hydrogen chloride of the mass fraction 30% of 19.11g is added into the dropping funel of 100ml
157.8mmol).Above-mentioned dropping funel is mounted on above-mentioned three-necked flask, is dripped above-mentioned aqueous hydrochloric acid solution under cold
Enter in above-mentioned aqueous dimethylamine, the hydrochloride of dimethyl amine is modulated in above-mentioned three-necked flask.Into above-mentioned three-necked flask
5.56g (185mmol) paraformaldehyde is added, the 2- indone of 9.0g (61.6.mmol) is then added.Nitrogen displacement is warming up to 85~
90 DEG C are reacted 3 hours, and reaction solution is obtained.And gas chromatographic analysis is carried out to reaction solution, the conversion ratio of confirmation 2- indone is 98%,
The solution containing A2-1 is obtained, can directly be carried out in next step.
(2) synthesis of compound A2-3
Above-mentioned reaction solution is cooled to 50 DEG C, the dimethyl aqueous amine of methyl cellosolve (50ml) and mass fraction 50% is added
Solution 2.24g (containing dimethyl amine 24.8mmol) and cyclopentadiene 14.26g (containing cyclopentadiene 216mmol), obtains mixed liquor.
Nitrogen displacement is warming up to 115~120 DEG C, and reacts 1.5h at this temperature, after reaction, above-mentioned mixed liquor is cooled to room
Warm (25 DEG C).Then, above-mentioned mixed liquor is transferred in the separatory funnel of 500ml, is extracted with normal heptane (150ml), is used again
Normal heptane (80ml) extraction, obtains normal heptane extracting solution after merging.The normal heptane extracting solution is successively used to the hydrogen of mass fraction 5%
Aqueous solution of sodium oxide (50ml) washs 1 time, is washed 1 time with the aqueous hydrochloric acid solution (50ml) of mass fraction 5%.Use mass fraction
5% sodium bicarbonate aqueous solution (50ml) washs 1 time, is washed 1 time with saturated salt solution (50ml).Extracting solution after washing is used
Anhydrous magnesium sulfate is dry, then filters out anhydrous magnesium sulfate, is spin-dried for obtaining grease 19.2g, then carry out short-path distillation (129 DEG C,
11mmHg), A1-3 12.5g, GC:98%, yield 67% are obtained.Cl-MS (m/z): 303.1617 (M+1).
(3) synthesis of compound A2-4
Methanol 364g, chloroform 62g, copper chloride (II) 136g (1011mmol), chlorine are added into the reaction vessel of capacity 1L
Change palladium 6g (33.7mmol), is stirred.After atmosphere gas in system is replaced into carbon monoxide, dissolved with dropwise addition in 3 hours
The solution of compound A2-3 in chloroform, wherein chloroform is 178g, and compound A2-3 is 20.33g (67.3mmol), 20~
25 DEG C react it 4 hours.Then, the atmosphere in system is replaced into argon gas from carbon monoxide, later from reaction mixture
Solvent is distilled off, adds chloroform 621g.And then it is repeated twice same operation.Then obtained suspension is filtered to remove not
Molten object.Obtained solution is cleaned 3 times with saturated sodium bicarbonate aqueous solution 324g, and then is cleaned 3 times with pure water 324g, it
Anhydrous magnesium sulfate 2.7g, active carbon 2.7g are added in backward organic layer and is stirred.Then, it is depressurized after filtering solution
Concentration, obtains white solid 51g.Then, by silica gel chromatography, (developing solvent is hexane: ethyl acetate=10: 1 (capacity
Than)) purified, obtain the A2-425.34g as white solid.Purity 98%, yield 70% based on HPLC analysis.Cl-
MS (m/z): 539.2204 (M+1).
(4) synthesis of compound A2
A2-4 6.41g (11.9mmol), formic acid 26.3g, p-methyl benzenesulfonic acid are put into the reaction vessel of capacity 100mL
Monohydrate 47mg (0.24mmol) reacts it 30 hours.After reaction, reaction solution is depressurized dense
Toluene 30g is added in contracting into concentrate.It is repeated 6 times the operation, formic acid is completely distilled off removing.Obtained suspension is filtered,
It after obtained solid is cleaned with toluene 30g, is dried in vacuo at 80 DEG C, obtains Off-white solid 4.7g.Later,
It is recrystallized using acetic anhydride, and then is recrystallized using n,N-dimethylacetamide, obtain the change as white solid
Close object A2 4.3g.Purity 98.3%, yield 81% based on 1H-MMR analysis.1Cl-MS (m/z): 447.13 (M+1).
The synthesis of compound B-11
The synthetic line of prepare compound B1 is as follows:
Specific step is as follows:
(1) synthesis of compound B-11-1
The aqueous dimethylamine 13.66g that mass fraction 50% is added into the three-necked flask of 250ml (contains dimethyl amine
151mmol).Aqueous hydrochloric acid solution (the containing hydrogen chloride of the mass fraction 30% of 19.11g is added into the dropping funel of 100ml
157.8mmol).Above-mentioned dropping funel is mounted on above-mentioned three-necked flask, is dripped above-mentioned aqueous hydrochloric acid solution under cold
Enter in above-mentioned aqueous dimethylamine, the hydrochloride of dimethyl amine is modulated in above-mentioned three-necked flask.Into above-mentioned three-necked flask
5.56g (185mmol) paraformaldehyde is added, the 2- indone of 11.2g (61.6.mmol) is then added.Nitrogen displacement is warming up to 85
~90 DEG C are reacted 3 hours, and reaction solution is obtained.And gas chromatographic analysis is carried out to reaction solution, the conversion ratio of confirmation 2- indone is
98%, the solution containing B1-1 is obtained, can directly be carried out in next step.
(2) synthesis of compound B-11-3
Above-mentioned reaction solution is cooled to 50 DEG C, the dimethyl aqueous amine of methyl cellosolve (50ml) and mass fraction 50% is added
Solution 2.24g (containing dimethyl amine 24.8mmol) and cyclopentadiene 14.26g (containing cyclopentadiene 216mmol), obtains mixed liquor.
Nitrogen displacement is warming up to 115~120 DEG C, and in this thermotonus 1.5h, after reaction, above-mentioned mixed liquor is cooled to room temperature
(25℃).Then, above-mentioned mixed liquor is transferred in the separatory funnel of 500ml, is extracted with normal heptane (150ml), again with just
Heptane (80ml) extraction, merging obtain normal heptane extracting solution.The normal heptane extracting solution is successively used to the hydroxide of mass fraction 5%
Sodium water solution (50ml) washs 1 time, is washed 1 time with the aqueous hydrochloric acid solution (50ml) of mass fraction 5%.With mass fraction 5%
Sodium bicarbonate aqueous solution (50ml) washs 1 time, is washed 1 time with saturated salt solution (50ml).By the extracting solution after washing with anhydrous
Magnesium sulfate is dry, then filters out anhydrous magnesium sulfate, is spin-dried for obtaining grease 26g, then carry out short-path distillation (129 DEG C,
11mmHg), B1-3 14.9g is obtained.GC:98%, yield 72%.Cl-MS (m/z): 339.1617 (M+1).
(3) synthesis of compound B-11-4
Methanol 364g, chloroform 62g, copper chloride (II) 136g (1011mmol), chlorine are added into the reaction vessel of capacity 1L
Change palladium 6g (33.7mmol), is stirred.After atmosphere gas in system is replaced into carbon monoxide, dissolved with dropwise addition in 3 hours
The solution of compound B2-3 in chloroform, wherein chloroform is 178g, and compound B2-3 is 22.74g (67.3mmol), 20~
25 DEG C react it 4 hours.Then, the atmosphere in system is replaced into argon gas from carbon monoxide, later from reaction mixture
Solvent is distilled off, adds chloroform 621g.And then it is repeated twice same operation.Then, obtained suspension is filtered to remove
Insoluble matter.Obtained solution is cleaned 3 times with saturated sodium bicarbonate aqueous solution 324g, and then is cleaned 3 times with pure water 324g,
Backward organic layer in anhydrous magnesium sulfate 2.7g be added, active carbon 2.7g and be stirred.Then, subtracted after filtering solution
Pressure concentration, obtains white solid 51g.Then, by silica gel chromatography, (developing solvent is hexane: ethyl acetate=10: 1 (capacity
Than)) purified, obtain the B1-3 27.45g as white solid.Purity 98%, yield 71% based on HPLC analysis.
Cl-MS (m/z): 575.2204 (M+1).
(1) synthesis of compound B-11
B1-4 6.83g (11.9mmol), formic acid 26.3g, p-methyl benzenesulfonic acid are put into the reaction vessel of capacity 100mL
Monohydrate 47mg (0.24mmol) reacts it 30 hours.After reaction, reaction solution is depressurized dense
Toluene 30g is added in contracting into concentrate.It is repeated 6 times the operation, formic acid is completely distilled off removing.Obtained suspension is filtered,
It after obtained solid is cleaned with toluene 30g, is dried in vacuo at 80 DEG C, obtains Off-white solid 4.7g.Later,
It is recrystallized using acetic anhydride, and then is recrystallized using n,N-dimethylacetamide, obtain the change as white solid
Close object B1 4.4g.Purity 98.7%, yield 77% based on 1H-MMR analysis.1Cl-MS (m/z): 483.13 (M+1).
The application of anhydride compounds
Illustrate anhydride compounds of the present invention answering in clear polyimides field by the following examples
With.But the present invention is not limited to following embodiments.
Embodiment 1
Reaction vessel is exhausted using nitrogen in advance, 126.53g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), then 10.01g (50mmol) 4,4'- diaminodiphenyl ether (ODA) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;21.62g (50mmol) anhydride compounds A1 is gradually added again, is stirred to complete
After fully dissolved, insulation reaction for 24 hours, to obtain 20wt% polyimides acid solution.
After reaction, it is separately added into the equimolar acetic anhydride of carboxylic acid group and isoquinolin, the DMAc removed water is added, is tuned into
The solution of 15~18wt%;On the glass substrate by obtained polyimide acid solution coating, it is transferred on needle plate after prebake,
It transfers in baking oven, is heat-treated 30min at 150 DEG C/250 DEG C/300 DEG C/350 DEG C respectively, hot imidization is carried out, to make
There must be the Kapton of about 25 μ m thicks.
Embodiment 2
Reaction vessel is exhausted using nitrogen in advance, 129.34g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), then 10.01g (50mmol) 4,4'- diaminodiphenyl ether (ODA) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;22.32g (50mmol) anhydride compounds A2 is gradually added again, is stirred to complete
After fully dissolved insulation reaction for 24 hours, to obtain 20wt% polyimides acid solution.
Then, the Kapton of 25 μ m-thicks is prepared in such a way that embodiment 1 is identical.
Embodiment 3
Reaction vessel is exhausted using nitrogen in advance, 136.54g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), then 10.01g (50mmol) 4,4'- diaminodiphenyl ether (ODA) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;24.12g (50mmol) anhydride compounds B1 is gradually added again, is stirred to complete
After fully dissolved, insulation reaction for 24 hours, to obtain 20wt% polyimides acid solution.
Then, the Kapton of 25 μ m-thicks is prepared in such a way that embodiment 1 is identical.
Embodiment 4
Reaction vessel is exhausted using nitrogen in advance, 139.71g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), respectively by 5.00g (25mmol) 4,4'- diaminodiphenyl ether (ODA) and 8.00g
Bis- (trifluoromethyl) -4,4'- benzidines of (25mmol) 2,2'-) (TFMB) be fitted into and be dissolved in DMAc, stir at 25 DEG C
To being completely dissolved;Gradually add again bis- (3,4- dicarboxylic acids) hexafluoropropane dianhydrides (6FDA) of 11.11g (25mmol) 2,2'- and
10.81g (25mmol) anhydride compounds A1, stir to after being completely dissolved, insulation reaction for 24 hours, to obtain 20wt% polyamides
Imines acid solution.
Then, the Kapton of 25 μ m-thicks is prepared in such a way that embodiment 1 is identical.
Comparative example 1
Reaction vessel is exhausted using nitrogen in advance, 98.89g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), then 10.01g (50mmol) 4,4'- diaminodiphenyl ether (ODA) is packed into and is dissolved
In DMAc, stirred at 25 DEG C to being completely dissolved;3,3 ', 4,4 '-biphenyltetracarboxyacid acid two of 14.71g (50mmol) is gradually added again
Acid anhydride (BPDA) is stirred to rear insulation reaction is completely dissolved for 24 hours, to obtain 20wt% polyimides acid solution.
Then, the Kapton of 25 μ m-thicks is prepared in such a way that embodiment 1 is identical.
Comparative example 2
Reaction vessel is exhausted using nitrogen in advance, 140.90g n,N-dimethylacetamide is added after 30min
(DMAc is removed water with molecular sieve for 24 hours in advance), then respectively by 8.00g (25mmol) 2,2 '-bis- (trifluoromethyl) -4,4 '-diamino
Biphenyl (TFMB) and 4,4 '-diaminodiphenyl ether (ODA) of 5.00g (25mmol) are fitted into and are dissolved in DMAc, stir at 25 DEG C
To being completely dissolved;22.21g (50mmol) 2,2 '-bis- (3,4- dicarboxylic acids) hexafluoropropane dianhydrides (6FDA), stirring are gradually added again
To rear insulation reaction is completely dissolved for 24 hours, so that 20wt% polyimides acid solution be made.
Then, the Kapton of 25 μ m-thicks is prepared in such a way that embodiment 1 is identical.
Summarize by Kapton characteristic, result obtained in method described below testing example and comparative example
In table 1.
(1) thermal linear expansion coefficient (CTE)
According to thermomechanical analysis, polyamides is measured using thermomechanical analyzer (TA Instrument company, model Q400)
The thermal expansion coefficient of imines film.The condition of measurement is as follows: specimen size: 16mm × 4mm, atmosphere: under nitrogen atmosphere;Temperature: add
Heating rate 10 DEG C/min, 50 to 250 DEG C of scanning range;Drawing force: 0.05N, 50 to 200 DEG C of value range.
(2) yellowness index
Using ultraviolet spectrophotometer (Varian company, model C ary100), according to ASTM E313 canonical measure.
(3) light transmittance
The visible light transmittance rate of polyimide film is surveyed with ultraviolet spectrophotometer (Varian company, model C ary100)
.
(4) glass transition temperature (Tg)
It is measured using scan-type heating differential analysis instrument (TA Instrument company, model Q400).Atmosphere: under nitrogen atmosphere;
Temperature: 5 DEG C/min of the rate of heat addition;Drawing force: 0.05N;Sample size: 16mm × 4mm.
1 embodiment of table and the made Kapton parameter of comparative example
It can be seen from the data in table 1 by Examples 1 to 3 compared with comparative example 1 (traditional PI formula), light transmittance
Much higher than comparative example, illustrate that dicarboxylic anhydride of the invention has obvious optical property advantage;By embodiment 4 and (the transparent PI of comparative example 2
Formula) compare, dicarboxylic anhydride of the present invention has still embodied excellent optical property.
In conclusion anhydride compounds of the present invention are used for polyimides preparation, polyamides Asia can be effectively improved
The light transmittance of amine film is, it can be achieved that PI film to the optical characteristics of light transmittance >=85% of 550mm light wave, while having both preferable
Heat resistance.Illustrate that the anhydride compounds have on the basis of transparent polyimide film field application, is filled in Flexible Displays
It sets and has a good application prospect with photoelectric fields such as optical transparent films.
Although the present invention is disclosed as above with embodiment, it is not intended to limit the invention, anyone skilled in the art,
Without departing from the spirit and scope of the present invention, any change or equivalent replacement can be made, therefore protection scope of the present invention should be with
Subject to the range that the claim of this application is defined.
Claims (10)
1. a kind of anhydride compounds, which is characterized in that indicated with any one in following [chemical formula A] or [chemical formula B]:
[chemical formula A]
[chemical formula B]
In [the chemical formula A] and [chemical formula B], the XI、X2、X3、X4、X5、X6、X7、X8It is identical or different with n, wherein n
=0-12 integer;
The XIIt is CmR1, S atom, N atom or O atom, m=0 or 1;
The X2It is CmR2, S atom, N atom or O atom, m=0 or 1;
The X3It is CmR3, S atom, N atom or O atom, m=0 or 1;
The X4It is CmR4, S atom, N atom or O atom, m=0 or 1;
The X5It is CmR5, S atom, N atom or O atom, m=0 or 1;
The X6It is CmR6, S atom, N atom or O atom, m=0 or 1;
The X7It is CmR7, S atom, N atom or O atom, m=0 or 1;
The X8It is CmR8, S atom, N atom or O atom, m=0 or 1;
The substituent R1To R10Respectively it is identical or different, and be independently from each other hydrogen, heavy hydrogen, halogen, be substituted or not
The alkene that alkyl or alkoxy that substituted carbon atom number is 1 to 30, substituted or unsubstituted carbon atom number are 2 to 30
Alkynyl that base, substituted or unsubstituted carbon atom number are 2 to 30, substituted or unsubstituted carbon atom number are 3 to 30
Naphthenic base or cycloalkenyl, substituted or unsubstituted carbon atom number be 6 to 30 aryl or aryloxy group, be substituted or not
The fragrant sulphur oxygen that alkane-sulfur oxyl that substituted carbon atom number is 1 to 30, substituted or unsubstituted carbon atom number are 6 to 30
Alkylamino radical that base, substituted or unsubstituted carbon atom number are 1 to 30, substituted or unsubstituted carbon atom number be 6 to
30 aryl amine, substituted or unsubstituted and has miscellaneous original the aryl that substituted or unsubstituted carbon atom number is 6 to 50
Alkyl tin groups, alkyl silane groups that heteroaryl that the carbon atom number of sub- O, N or S are 2 to 50, carbon atom number are 1 to 24, carbon atom number be 6 to
24 aryl-silane base, substituted or unsubstituted boryl, substituted or unsubstituted phosphoryl, amino, sulfydryl, nitre
Any one in base, seleno, amide groups, ether and ester group;
The M is the aromatic ring that substituted or unsubstituted carbon atom number is 2 to 30 or heteroaromatic, 1,4- cyclohexadiene or miscellaneous
The cyclohexadiene that atom replaces.
2. anhydride compounds according to claim 1, which is characterized in that the XI、X2、X3、X4、X5、X6、X7And X8It is identical
Or it is different, it is each independently selected from-CH-, S atom, N atom or O atom, n=0 or 1;The M is to substituted or unsubstituted
Phenyl ring or heteroaromatic, the heteroaromatic have hetero atom O, N or S.
3. the preparation method of anhydride compounds of any of claims 1 or 2, which is characterized in that
The preparation method such as chemistry anhydride compounds shown in formula A the following steps are included:
(1) using compound A-1 as raw material, diamine compound A-2 is obtained by Mannich reaction;
(2) make compound A-2 that the reaction of deamination methyl occur, obtain bifunctional vinyl compound A-3;
(3) make compound A-3 that retaining ring occur with cyclopentadiene to react, obtain bicyclo hexene compound A-4;
(4) under palladium chtalyst, make compound A-4 that Infectious disease reaction occur, obtain compound A-5;
(5) make compound A-5 that hydrolysis and dehydration occur, obtain compound A-6;
The preparation methods of the anhydride compounds as shown in chemical formula B the following steps are included:
(1) using compound B-1 as raw material, diamine compound B-2 is obtained by Mannich reaction;
(2) make compound B-2 that the reaction of deamination methyl occur, obtain bifunctional vinyl compound B-3;
(3) make compound B-3 that retaining ring occur with cyclopentadiene to react, obtain bicyclo hexene compound B-4;
(4) under palladium chtalyst, make compound B-4 that Infectious disease reaction occur, obtain compound B-5;
(5) make compound B-5 that hydrolysis and dehydration occur, obtain compound B-6.
4. preparation method according to claim 3, which is characterized in that in step (1), be make compound A-1 or B-1 with it is secondary
Amine salt and formaldehyde reaction,
The secondary amine salt is hydrochloride, sulfate or the acetate of secondary amine, and the molar ratio of A-1 or B-1 and secondary amine salt is 1.0:2.0
~10.0;The molar ratio of A-1 or B-1 and formaldehyde is 1.0:2.0~10.0;
And/or the reaction condition are as follows: reacted 0.5~10 hour under inert atmosphere, reaction temperature is 30~180 DEG C, preferably
85~95 DEG C;
And/or it is described reaction carry out in organic solvent, the organic solvent be selected from tetrahydrofuran, methanol, ethyl alcohol, isopropanol,
Butanol, second eyeball, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, methylene chloride, a chlorine trifluoro
At least one of methane, preferably isopropanol.
5. preparation method according to claim 3, which is characterized in that in step (2) and (3), be added in reaction process graceful
The molar ratio of the uncommon alkali of Buddhist nun and cyclopentadiene, the compound A-3 or B-3 and cyclopentadiene is 1.0:2.0~10.0;
And/or the reaction condition are as follows: water-bath 0.5~10 hour under inert atmosphere, reaction temperature are 120~125 DEG C,
Preferably 85~95 DEG C.
6. preparation method according to claim 3, which is characterized in that in step (4), in palladium catalyst and copper catalyst
Under effect, react alcoholic compound and carbon monoxide with compound A-4 or B-4;
And/or the mass ratio of the compound A-4 or B-4 and alcoholic compound is 1:1~100, preferably 1:5~50;
And/or the molar ratio of the compound A-4 or B-4 and palladium catalyst is 1:0.001~1, preferably 1:0.01~0.5;
And/or the molar ratio of the compound A-4 or B-4 and copper catalyst is 1:1.0~50, preferably 1:4.0~20.
7. preparation method according to claim 3, which is characterized in that in step (5), be under the action of acid catalyst,
The compound A-5 or B-5 is placed in heating stirring in organic solvent, brings it about dehydration;
And/or the heating temperature is 50~130 DEG C, preferably 80~120 DEG C;
And/or the mass ratio of the compound A-5 or B-5 and the organic solvent is 1:0.1~100, preferably 1:1~10.
8. any one of anhydride compounds according to claim 1 or 2 or claim 3~7 method is prepared
The application of anhydride compounds, which is characterized in that the anhydride compounds are used to prepare transparent polyimide film.
9. the application of anhydride compounds according to claim 8, which is characterized in that the transparent polyimide film
The dicarboxylic anhydride chemical combination being prepared by any one of anhydride compounds as claimed in claim 1 or 2 or claim 3~7 method
Object, other aliphatic or aromatic diacid acid anhydride compound and diamine compound are prepared.
10. the application of anhydride compounds according to claim 8 or claim 9, which is characterized in that the diamine compound choosing
From 4,4 '-diaminodiphenyl ethers, p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 4,4 '-diaminodiphenylmethane, anti-form-1,4-
At least one of cyclohexanediamine and 2,2 '-bis- (trifluoromethyl) -4,4 '-benzidines).
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Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006056944A (en) * | 2004-08-18 | 2006-03-02 | Chisso Corp | Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer |
CN102906097A (en) * | 2010-02-09 | 2013-01-30 | 吉坤日矿日石能源株式会社 | Norbornane-2-spiro-cycloalkanone-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-cycloalkanone-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid and ester thereof, method for producing norbornane-2-spiro |
JP2013105063A (en) * | 2011-11-15 | 2013-05-30 | Jsr Corp | Liquid crystal aligning agent, and liquid crystal display element |
CN103733274A (en) * | 2011-08-08 | 2014-04-16 | 吉坤日矿日石能源株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
US20150086753A1 (en) * | 2012-09-26 | 2015-03-26 | Jx Nippon Oil & Energy Corporation | NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, NORBORNANE-2-SPIRO-a- CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC ACID AND ESTER THEREOF, METHOD FOR PRODUCING NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, POLYIMIDE OBTAINED BY USING THE SAME, AND METHOD FOR PRODUCING POLYIMIDE |
CN104583275A (en) * | 2012-08-31 | 2015-04-29 | 吉坤日矿日石能源株式会社 | Polyimide, and alicyclic tetracarboxylic acid dianhydride for use in production of same |
JP2015137234A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | Method for producing carboxylic acid anhydride |
JP2017115164A (en) * | 2017-03-30 | 2017-06-29 | Jxtgエネルギー株式会社 | Thermosetting resin composition and epoxy resin cured product |
JP2017155163A (en) * | 2016-03-03 | 2017-09-07 | Jxtgエネルギー株式会社 | Tetracarboxylic acid dianhydride, polyimide and method for producing the same |
KR20180086903A (en) * | 2017-01-24 | 2018-08-01 | 연세대학교 원주산학협력단 | Nonvolatile resistive memory device based on polyimide/graphene oxide nanocomposite |
JP2019059959A (en) * | 2018-08-03 | 2019-04-18 | Jxtgエネルギー株式会社 | Tetracarboxylic acid dianhydride, polyimide precursor resin, polyimide, polyimide precursor resin solution, polyimide solution and polyimide film |
CN110177794A (en) * | 2017-04-28 | 2019-08-27 | Jxtg能源株式会社 | Tetracarboxylic dianhydride, polyimides forerunner resin and its solution and polyimides and its solution |
WO2019163703A1 (en) * | 2018-02-21 | 2019-08-29 | Jxtgエネルギー株式会社 | Polyimide precursor resin composition |
-
2019
- 2019-09-02 CN CN201910822809.5A patent/CN110511229A/en active Pending
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006056944A (en) * | 2004-08-18 | 2006-03-02 | Chisso Corp | Tetracarboxylic dianhydride, polymer using the same as raw material, varnish, aligning film and liquid crystal display element using the polymer |
CN102906097A (en) * | 2010-02-09 | 2013-01-30 | 吉坤日矿日石能源株式会社 | Norbornane-2-spiro-cycloalkanone-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, norbornane-2-spiro-cycloalkanone-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid and ester thereof, method for producing norbornane-2-spiro |
CN103733274A (en) * | 2011-08-08 | 2014-04-16 | 吉坤日矿日石能源株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
JP2013105063A (en) * | 2011-11-15 | 2013-05-30 | Jsr Corp | Liquid crystal aligning agent, and liquid crystal display element |
CN104583275A (en) * | 2012-08-31 | 2015-04-29 | 吉坤日矿日石能源株式会社 | Polyimide, and alicyclic tetracarboxylic acid dianhydride for use in production of same |
US20150086753A1 (en) * | 2012-09-26 | 2015-03-26 | Jx Nippon Oil & Energy Corporation | NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, NORBORNANE-2-SPIRO-a- CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC ACID AND ESTER THEREOF, METHOD FOR PRODUCING NORBORNANE-2-SPIRO-a-CYCLOALKANONE-a'-SPIRO-2"-NORBORNANE-5,5",6,6"-TETRACARBOXYLIC DIANHYDRIDE, POLYIMIDE OBTAINED BY USING THE SAME, AND METHOD FOR PRODUCING POLYIMIDE |
JP2015137234A (en) * | 2014-01-20 | 2015-07-30 | Jx日鉱日石エネルギー株式会社 | Method for producing carboxylic acid anhydride |
JP2017155163A (en) * | 2016-03-03 | 2017-09-07 | Jxtgエネルギー株式会社 | Tetracarboxylic acid dianhydride, polyimide and method for producing the same |
KR20180086903A (en) * | 2017-01-24 | 2018-08-01 | 연세대학교 원주산학협력단 | Nonvolatile resistive memory device based on polyimide/graphene oxide nanocomposite |
JP2017115164A (en) * | 2017-03-30 | 2017-06-29 | Jxtgエネルギー株式会社 | Thermosetting resin composition and epoxy resin cured product |
CN110177794A (en) * | 2017-04-28 | 2019-08-27 | Jxtg能源株式会社 | Tetracarboxylic dianhydride, polyimides forerunner resin and its solution and polyimides and its solution |
WO2019163703A1 (en) * | 2018-02-21 | 2019-08-29 | Jxtgエネルギー株式会社 | Polyimide precursor resin composition |
JP2019059959A (en) * | 2018-08-03 | 2019-04-18 | Jxtgエネルギー株式会社 | Tetracarboxylic acid dianhydride, polyimide precursor resin, polyimide, polyimide precursor resin solution, polyimide solution and polyimide film |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116970276A (en) * | 2023-09-25 | 2023-10-31 | 北京八亿时空液晶科技股份有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
CN116970276B (en) * | 2023-09-25 | 2024-01-09 | 上海八亿时空先进材料有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
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