CN115521243A - Tri-functionality cross-linking agent and preparation method and application thereof - Google Patents

Tri-functionality cross-linking agent and preparation method and application thereof Download PDF

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CN115521243A
CN115521243A CN202211177020.7A CN202211177020A CN115521243A CN 115521243 A CN115521243 A CN 115521243A CN 202211177020 A CN202211177020 A CN 202211177020A CN 115521243 A CN115521243 A CN 115521243A
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crosslinking agent
cross
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absorption peak
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CN115521243B (en
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公聪聪
李铭新
唐衍超
孟凡兴
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Bomi Technology Co ltd
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    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
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    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/549—Organic PV cells

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Abstract

The application discloses a threeA functionality cross-linking agent, a preparation method and application thereof, belonging to the field of functional polymer materials. A trifunctional crosslinking agent, said trifunctional crosslinking agent having a structure according to formula i:
Figure DDA0003864948320000011
wherein W is an organic group containing an N-heterocycle; x 1 、X 2 、X 3 Are respectively and independently selected from any one of the structures shown in general formulas II to IV
Figure DDA0003864948320000012
In the general formulas II to IV: r is 1 An alkyl group or an alkoxy group having 1 to 20 carbon atoms; r is 2 、R 3 Is hydrogen atom or organic group with 1-6 carbon atoms; r 4 Is an alkynyl-containing organic group. The trifunctional cross-linking agent contains double bonds or alkynyl, N heterocyclic groups and amide acid ester structures. The crosslinking agent has low dielectric constant and high heat resistance.

Description

Tri-functionality cross-linking agent, and preparation method and application thereof
Technical Field
The application relates to a trifunctional cross-linking agent, a preparation method and application thereof, and belongs to the field of functional polymer materials.
Background
The flexible display has the characteristics of lightness, thinness and insusceptibility to breakage, has various appearance forms and infinite product design possibility, and is the main research direction of the current display. Compared with a Liquid Crystal Display (LCD), the Organic Light Emitting Diode (OLED) display has a simple structure and is more suitable for manufacturing a flexible display. OLED displays have reached 160 billion dollars in market size in 2020. The OLED has high luminous efficiency and high contrast, and can be widely applied to the aspects of mobile phones, digital cameras, navigators, commercial labels and the like.
Polyimide has excellent light transmittance, thermal properties and mechanical properties, and is widely used in the fields of electronics, vehicles, airplanes, semiconductors and the like. The low-temperature curing type photosensitive polyimide can be coated on a glass substrate of an OLED device, a layer of polyimide film can be newly formed on the surface of the substrate through low-temperature heat treatment after patterns are engraved, and passivation effects such as insulation, water isolation, oxygen isolation and the like are achieved. Due to the special requirements of the OLED device, the performance requirements of the photosensitive polyimide coating adhesive for the OLED device are also very strict, such as low curing temperature, low dielectric constant, high heat resistance and the like.
At present, the researches on the photosensitive polyimide coating adhesive for the OLED device packaging layer mainly comprise the following steps: patent CN 109153841A discloses a resin composition prepared by introducing a phenol skeleton having a crosslinkable group and a phenol skeleton having no crosslinkable group into an alkali-resistant resin, which can provide a cured film having excellent chemical resistance, low stress and high elongation under low temperature curing conditions. Patent CN 108779251A uses alkali soluble resin with benzoxazole precursor structure and aliphatic group, thermal acid generator and antioxidant to prepare a cured film which can be cured by low temperature heat treatment and has excellent heat resistance, chemical resistance and elongation at break, and can be used as an insulating layer of an organic electroluminescent device. In addition, soluble polyimide or polyisoimide can be prepared to realize low-temperature curing of resin, but the solubility is poor and the application is limited. Patent CN 102047178B added with commercial thermal crosslinking agent made by bobble petrochemical company to improve tensile elongation of the cured film and show good adhesion and lithographic performance, but because this crosslinking agent is imidized structure, it has poor solubility in some low-solubility solvents such as EL and PGME, which are indispensable for improving uniformity of the cured film. In addition, the crosslinking agent of the pelletized petroleum only contains two polymerizable double bonds, and has certain defects in improving the film performance.
Disclosure of Invention
According to a first aspect of the present application, there is provided a trifunctional crosslinking agent having a structure containing a double bond or an alkynyl group capable of crosslinking reaction, which can generate crosslinking during the curing process of the composition to improve the film-forming property and increase the glass transition temperature. Meanwhile, the cross-linking agent contains an N heterocyclic group, and a nitrogen atom in the N heterocyclic group can be combined with hydrogen ions to form a complex, so that the dehydration cyclization reaction of the polyamic acid or polyamic acid ester can be promoted, and the curing temperature of the composition is further reduced. The cross-linking agent contains an amic acid ester structure, has high compatibility with heat-resistant resins such as polyamic acid, polyamic acid ester and the like, has better solubility in a solvent than a cross-linking agent with an imide structure, particularly in solvents such as gamma-butyrolactone, ethyl lactate, propylene glycol methyl ether and the like, can form a cross-linking network after being heated, greatly improves the heat resistance of a cured film, and can reduce the dielectric constant of the cured film due to the existence of N heteroatoms in the cross-linking network, thereby forming the low-dielectric and high-heat-resistant low-temperature curing type photosensitive polyimide composition.
A trifunctional crosslinker having a structure of formula i:
Figure BDA0003864948300000011
wherein W is an organic group containing an N-heterocycle;
X 1 、X 2 、X 3 are respectively and independently selected from any one of the structures shown in general formulas II to IV;
Figure BDA0003864948300000012
Figure BDA0003864948300000021
in the general formulae II to IV:
R 1 is alkyl or alkoxy of 1 to 20 carbon atoms;
R 2 、R 3 is hydrogen atom or organic group with 1-6 carbon atoms;
R 4 is an alkynyl-containing organic group.
Alternatively, R 2 、R 3 Is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
Alternatively, X 1 、X 2 、X 3 The same structure is adopted.
Alternatively, W is an organic group having 2 to 40 carbon atoms;
R 4 selected from alkynyl-containing organic groups having 2 to 20 carbon atoms;
R 4 selected from alkyl with 2-10 carbon atoms, alkoxy with 2-10 carbon atoms and phenyl with 2-20 carbon atoms.
Optionally, the N heterocycle is selected from one of triazine, triazole, pyridine, carbazole, pyrimidine, imidazole, and benzothiazole.
Alternatively, R 1 One selected from methyl, ethyl, propyl, n-butyl, tert-butyl and hydroxyethyl methacrylate.
Alternatively, R 4 Is selected from
Figure BDA0003864948300000022
One kind of (1).
Alternatively, W is selected from the following structural formulae:
Figure BDA0003864948300000023
according to a second aspect of the present application, there is provided a process for the preparation of a trifunctional crosslinker.
A method of preparing a trifunctional crosslinking agent, comprising the steps of:
s1, reacting a mixture containing anhydride, an N heterocyclic compound and an organic solvent to obtain a precursor liquid;
and S2, adding an esterification reagent into the precursor liquid, and reacting II to obtain the tri-functionality cross-linking agent.
Optionally, in step S1, the anhydride is selected from any one of the following structures:
Figure BDA0003864948300000031
wherein R is 2 、R 3 、R 4 As described for R 2 、R 3 、R 4 The range of (1).
Optionally, the anhydride contains a double bond or an alkynyl group.
Alternatively, the anhydride containing a double bond is 5-allyl nadic anhydride, allyl succinic anhydride.
Alternatively, the anhydride containing an alkynyl group is 4-ethynyl phthalic anhydride, methylacetylphthalic anhydride.
Alternatively, in step S1, the N-heterocyclic compound is selected from compounds represented by the following structures:
Figure BDA0003864948300000032
alternatively, in step S1, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diglyme, and diethylene glycol dimethylether.
Alternatively, in step S1, the molar ratio of the anhydride to the N-heterocyclic compound is 3:0.9 to 1.1.
Alternatively, the molar ratio of the anhydride to the N-heterocyclic compound is 3:0.95 to 1.05.
Alternatively, the molar ratio of the anhydride to the N-heterocyclic compound is independently selected from 3:0.90, 3:0.92, 3:0.95, 3:0.97, 3:1.00, 3:1.02, 3:1.05, 3:1.07, 3:1.10 or a range between any two.
Optionally, in step S1, the mass ratio of the acid anhydride to the organic solvent is 5 to 50:100.
alternatively, in step S1, the mass ratio of the acid anhydride to the organic solvent is independently selected from 5: 100. 6: 100. 7: 100. 8: 100. 9: 100. 10: 100. 15: 100. 20: 100. 25: 100. 30: 100. 35: 100. 40: 100. 45, and (2) 45: 100. 50:100, or any range therebetween.
Alternatively, in step S1, the conditions of reaction i are as follows:
the temperature is 10-150 ℃;
the time is 3-24 h.
Optionally, the temperature is independently selected from any value or range of values between any two of 10 ℃,20 ℃, 30 ℃,40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
Optionally, the time is independently selected from any of 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, or a range between any two.
Optionally, in step S2, the esterification reagent is selected from at least one of N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dineopentylbutyl acetal, N-dimethylformamide di-tert-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholine \28355hydrochloride, hydroxyethyl methacrylate, 4-nitrobenzyl alcohol.
Optionally, the molar ratio of the addition amount of the esterification reagent in the step S2 to the addition amount of the acid anhydride in the step S1 is 1 to 5:1.
optionally, the molar ratio of the addition amount of the esterification reagent in the step S2 to the addition amount of the acid anhydride in the step S1 is 1.2 to 3:1.
alternatively, the molar ratio of the amount of esterification reagent added in step S2 to the amount of anhydride added in step S1 is independently selected from 1.0: 1. 1.2: 1. 1.4: 1. 1.6: 1. 1.8: 1. 2.0: 1. 2.2: 1. 2.4: 1. 2.6: 1. 2.8: 1. 3.0: 1. 3.2: 1. 3.4: 1. 3.6: 1. 3.8: 1. 4.0: 1. 4.2: 1. 4.4: 1. 4.6: 1. 4.8: 1. 5.0:1, or a range of values between any two.
Alternatively, in step S2, the conditions of reaction ii are as follows:
the temperature is 20-80 ℃;
the time is 2-24 h.
Optionally, the temperature is independently selected from any value of 20 ℃, 30 ℃,40 ℃, 50 ℃, 60 ℃, 70 ℃,80 ℃ or a range value between any two.
Alternatively, the time is independently selected from any of 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, or a range between any two.
On the other hand, the invention provides a preparation method of the N-heterocyclic trifunctional cross-linking agent, which comprises the following steps:
SP1: weighing a certain amount of N-containing heterocyclic triamine and dissolving the N-containing heterocyclic triamine into a certain amount of solvent.
SP2: adding a certain amount of double bond or alkynyl-containing anhydride into an SP1 reaction system, and reacting for 3-24 h at the temperature of 10-150 ℃.
SP3: after the SP2 reaction is finished, adding an esterification reagent into the reaction solution, and reacting for 2-24 h at the temperature of 20-80 ℃.
SP4: and after the reaction is finished, pouring the reaction liquid into deionized water, and separating out to obtain a crosslinking agent precipitate. And (3) washing the crosslinking agent precipitate with deionized water for three times after filtering, and drying for 36-120 h under the vacuum condition at the temperature of 40-100 ℃ to obtain the N heterocyclic ring-containing trifunctional crosslinking agent.
Further, the reaction temperature of SP2 is preferably 50 ℃ to 120 ℃, more preferably 70 ℃ to 90 ℃.
Further, the reaction temperature of SP4 is preferably 25 to 50 ℃, and is more preferably 30 to 40 ℃ in consideration of both the esterification efficiency and the imidization side reaction.
Furthermore, the N-heterocyclic tri-functionality cross-linking agent contains double bonds or alkynyl, can generate thermal cross-linking reaction under a certain temperature condition, and can be matched with a catalyst for improving the cross-linking effect or reducing the cross-linking temperature. Besides the crosslinkable functional group, the main body of the crosslinking agent is of an N-containing heterocyclic structure, and the existence of nitrogen atoms on the N heterocyclic ring can enhance the functionality of the crosslinking agent. In addition, the cross-linking agent has an amic acid ester structure, has better stability than a cross-linking agent with an amic acid structure, better solubility than imides and wider application range. The N-heterocyclic trifunctional cross-linking agent can be used as an additive to be applied to materials with polymers such as polyamic acid, polyamic acid ester, polyimide, polybenzoxazole precursor, polybenzoxazole, polyamide, polybenzimidazole, polybenzothiazole, phenolic resin, polyacrylate and the like as subject structures, can show different functional characteristics in different polymer materials, and can be adjusted in addition amount according to different application fields and application requirements or used in a compounding way with other different types of catalysts and additives.
According to a third aspect of the present application, there is provided a photosensitive resin composition.
A photosensitive resin composition comprising the following components:
a component a: at least one of polyamic acid and polyamic acid ester;
and (b) component b: a trifunctional crosslinking agent;
and (c) component: a photosensitizer;
a component d: a solvent;
and (e) component: at least one of a silane coupling agent, a leveling agent and a defoaming agent;
the trifunctional crosslinker is selected from the trifunctional crosslinkers described above.
Optionally, the mass ratio of component a to component b is 100:0.5 to 30.
Optionally, the mass ratio of component a to component b is 100:5 to 20.
Further, the preparation method of the photosensitive resin composition comprises the following steps:
uniformly mixing the component a, the component b, the component c and the component d according to a certain proportion, then adding the component e, uniformly mixing to obtain a polymer solution with a certain viscosity, filtering the polymer solution by using a filter with the pore size of 0.1-5 mu m, and removing impurities to obtain the photosensitive composition.
Further, the component a is a polyimide acid and polyimide acid ester structure shown in a general formula (8):
Figure BDA0003864948300000051
further, in the general formula (8), X 1 A 4-valent organic group having 4 to 40 carbon atoms; y is 1 An organic group having a valence of 2 and having 2 to 40 carbon atoms; r 5 And R 6 Each independently represents a hydrogen atom or a saturated aliphatic group or an unsaturated aliphatic group having 1 to 10 carbon atoms; n represents an integer of 2 to 200.
The further component a is obtained by reacting dianhydride monomer, diamine monomer and esterification reagent.
<xnotran> , 4,4'- ,2,3,3', 4'- ,3,3',4,4 '- ,2,3'4,4 '- , ,2,2', 3,3'- ,2,2- (2,3- ) , A ,1,1- (2,3- ) ,2,2- (3,4- ) ,4,4' - ( ) ,9,9- (3,4- ) ,3,3,4,4- . </xnotran>
Further, the diamine monomer may be selected from: <xnotran> 2,2'- (3- -4 ) ,4,4' - ,2,2 '- ( ) -4,4' - ,4,4'- -2,2' - , , ,3,3'- ,2,2' - (3- -4- ) ,2,2 '- (3- -4- ) ,2,2- [4- -3- (3- ) ] ,2,2' - ( ) - (1,1 '- ) 4,4' - ,9,9- (4- ) ,2,2- (4- (4- )) ,2,2- (4- (4- ) ) ,3,3'- (2,3,5,6- -4- ) -4,4' - ,2,2 '- [4- (2,3,5,6- -4- ) -3- ] ,2,2' - [4- (2,3,5,6- -4- ) -3- ] ,1,3- (1- -3- ) -5- (2,3,5,6- - </xnotran> 4-vinylphenoxy) benzene and 1, 3-diaminophenoxy-5- (2, 3,5, 6-tetrafluoro-4-vinylphenoxy) benzene.
Further, the component b is a trifunctional cross-linking agent containing N heterocycle shown in structural formulas I-IV, and the mass ratio of the component a to the component b is 100:0.5 to 30;
preferably, the mass ratio of the component a to the component b is 100:5 to 20;
further, component c is a sensitizer, which varies depending on the component a of the photosensitive resin composition of the present invention.
First, a case where a negative type is desired will be described. In this case, a photopolymerization initiator is used as the c sensitizer, and a photoradical polymerization initiator is preferable, and for example, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or a mixture of 2 or more species can be used. Examples of the photopolymerization initiator include, but are not limited to, 1- (4-phenylthio-phenyl) -octa-1, 2-dione-2-oxime-0-benzoate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzil ketone, 4-benzoyl-4 '-methyl diphenyl ketone, fluorenone, 2' -diethoxyacetophenone, 2-hydroxy-2-methyl propiophenone, and 2-epoxyethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate. The above-mentioned photopolymer initiator species are more preferably oxime esters, particularly from the viewpoint of sensitivity.
Next, a case where a positive type is desired will be described. In this case, the photoacid generator is used as the c-sensitizer, specifically, a diazoquinone compound, an onium salt, a halogen-containing compound, and the like can be used, but from the viewpoint of solvent solubility and storage stability, an ester compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond is preferable, and as the polyhydroxy compound, there can be mentioned: 2, 6-dimethoxymethyl-4-tert-butylphenol, 2, 6-dimethoxy-p-cresol, 2, 6-diacetoxymethyl-p-cresol, tetrahydroxybenzophenone and the like, but are not limited thereto. Commercially available quinonediazide compounds are preferred, and examples thereof include NT-300, 4NT-350, 4NT-300 and HP-190 (manufactured by Toyo Synthesis industries, japan).
Further, the mass ratio of the component a to the component c is 100:0.1 to 30;
preferably, the mass ratio of the component a to the component c is 100:2 to 25;
the solvent of component d is one or more kinds of aromatic hydrocarbons such as N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, and the like.
Further, the mass ratio of the component a to the component d is 100:70 to 3000;
preferably, the mass ratio of the component a to the component d is 100:150 to 1500.
Further, examples of the silane coupling agent in component e include γ -glycidoxypropyltrimethoxysilane, (8-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3- (triethoxysilylthio) propyltrimethoxysilane, 3- (trimethoxysilyl) -1-propanethiol, γ -thiopropyltriethoxysilane (New Nanjing Xuanhao material, KH-580), 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 1-propyl-1- (triethoxysilyl) methylurea and the like.
Further, the mass ratio of the component a to the silane coupling agent is 100:0.1 to 30;
preferably, the mass ratio of the component a to the silane coupling agent is 100:0.1 to 15;
preferably, the mass ratio of the component a to the silane coupling agent is 100:0.5 to 10;
further, examples of the leveling agent include an acrylic leveling agent, an organic silicon leveling agent, and a fluorine-containing leveling agent.
Further, the mass ratio of the component a to the leveling agent is 100:0.1 to 10;
further, the defoaming agent can be industrial products of BYK-A530, BYK-A550 and Airex-920.
Further, the mass ratio of the component a to the defoaming agent is 100:0.1 to 10;
further, the photosensitive resin composition may further include additives such as a photoinitiator, a crosslinking agent, a polymerization inhibitor, etc. according to the application requirements, and the additives may be selected from the types disclosed in the prior art.
According to a fourth aspect of the present application, an OLED device is provided.
An OLED device includes a passivation insulating layer;
the passivation insulating layer is selected from the photosensitive resin composition described above.
The beneficial effects that this application can produce include:
1) The trifunctional cross-linking agent provided by the application contains an amic acid ester structure, has high compatibility with heat-resistant resins such as polyamic acid and polyamic acid ester, and meanwhile has better solubility in solvents than cross-linking agents with imide structures, especially gamma-butyrolactone, ethyl lactate, propylene glycol methyl ether and the like; the storage stability of the cross-linking agent is superior to that of the amide acid structure. The crosslinking agent has low dielectric constant and high heat resistance.
2) The photosensitive resin composition provided by the application can be used for packaging a semiconductor chip, can be used for improving the film forming property of a packaging layer, improves the glass transition temperature and the mechanical strength of the packaging layer, reduces the curing temperature of the packaging layer, and greatly improves the reliability and the reliability of the chip.
Drawings
FIG. 1 is a cross-sectional view of an OLED device of the present application.
FIG. 2 is an infrared spectrum at different curing temperatures of the photosensitive resin composition of example 13.
FIG. 3 is a graph showing the change in imidization rate at different curing temperatures.
List of components and reference numbers:
1-a glass substrate; 2-indium tin oxide; 3-passivating the insulating layer; 4-a light-emitting layer; 5-a cathode; 6-isolation column.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
(1) Infrared Spectrum testing
The synthesized crosslinker sample was tested using infrared spectrometer (Shimadzu, IRaffinity-1S) using KBr pellet method to determine whether the crosslinker of the invention was successfully prepared.
(2) Cross-linker purity test
The purity of the resultant crosslinking agent was tested using a liquid chromatograph (Shimadzu, LC-2030). And (3) chromatographic column: c18; wavelength: 254nm; column oven: 40 ℃; mobile phase: 0.1% phosphoric acid aqueous solution: acetonitrile =40:60, adding a solvent to the mixture; flow rate: 1.0ml/min.
(3) Crosslinker solubility test
Weighing 100g of gamma-butyrolactone (GBL), ethyl Lactate (EL) or Propylene Glycol Methyl Ether (PGME) in a beaker, putting the beaker into a water bath kettle, keeping the temperature to 30 ℃, weighing a certain amount of cross-linking agent, putting the cross-linking agent into the solvent, stirring and dissolving, adding a certain amount of cross-linking agent again until the solution reaches a saturated state, and calculating the total weight m of the dissolved cross-linking agent to be the solubility of the cross-linking agent in the solvent, wherein the unit is recorded as g/100g.
(4) Film forming property
A sample of the resin composition was uniformly coated on a silicon wafer, which was then placed on a 120 ℃ heating stage (HT-300 laboratory hotplate, kyoto instruments Co., ltd.) and soft-baked for 3 minutes to obtain a resin film having a film thickness of 10 to 20 μm. Then the film is placed in a vacuum oxygen-free oven (MOLZK-32D 1), under the protection of nitrogen atmosphere, heat-treated for 30 minutes at 170 ℃, heated to 250 ℃ for 1 hour, treated for 1 hour at 250 ℃, and then directly cooled to below 50 ℃ in an oven, and finally the cured film is obtained. And putting the silicon wafer with the curing film into a hydrofluoric acid solution, and corroding and demoulding the silicon wafer. The film forming property was evaluated by the following criteria.
"you": the resin composition can be formed into a film, has toughness and can not be broken when folded;
"good": the resin composition can be formed into a film, has toughness and is broken in double folding;
"poor": the resin composition failed to form a film and was in the form of chips.
When the film-forming property is "excellent", other test evaluations can be further performed.
(5) Curing film imidization test
The infrared spectrograms of the cured films at the curing temperatures of 250 ℃ and 350 ℃ were measured by ATR method using an infrared spectrometer (Shimadzu, IRaffinity-1S), and 1380cm was recorded -1 Intensity of a stretching vibration absorption peak at C-N bond, and 1500cm -1 Absorption peak intensity of benzene ring at (A).
The calculation formula of the imidization degree α is as follows:
Figure BDA0003864948300000071
(6) Glass transition temperature test
About 10g of the cured film obtained at 250 ℃ was placed in an aluminum standard container, and the glass transition temperature (Tg) was measured using a scanning calorimeter DSC-25 (TA instruments Watts, USA). First, pre-dried at 80 ℃ for 1 hour, and then measured at a temperature rise rate of 20 ℃/min.
(7) Tensile Strength test
A cured film prepared from the photosensitive resin composition was cut into sample strips having a length of 40 mm and a width of 5 mm, and the tensile strength of the sample strips was measured by DMA-850 (Tab instruments Watts, USA) at a temperature of 150 ℃, a tensile force in the range of 0-18N, and a rate of 3N/min.
(8) Dielectric constant test
NOVOCONTROL broadband dielectric and impedance spectrometer (BDS 40 germany) at 25 ℃, using an electrode diameter of 2 cm, test frequency range: 0.1Hz to 100MHz.
The abbreviations used in this application are as follows:
NMP: n-methyl pyrrolidone
GBL: gamma butyrolactone
EL: lactic acid ethyl ester
PGME: propylene glycol methyl ether
ODPA:4, 4-oxydiphthalic anhydride
Figure BDA0003864948300000072
HFHA:2, 2-bis [ 4-hydroxy-3- (3-amino) benzamido ] hexafluoropropane
Figure BDA0003864948300000073
BAHF:2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
ODA:4,4' -diaminodiphenyl ether
AD-1: 5-allyl nadic anhydride
Figure BDA0003864948300000074
AD-2: allyl succinic anhydride
Figure BDA0003864948300000075
AD-3: 4-ethynyl phthalic anhydride
Figure BDA0003864948300000076
AD-4: methylacetylenyl phthalic anhydride
Figure BDA0003864948300000081
IM-1:2,4, 6-triaminopyrimidines
Figure BDA0003864948300000082
IM-2:1,3, 5-triazine-2, 4, 6-triamines
Figure BDA0003864948300000083
IM-3:2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine
Figure BDA0003864948300000084
IM-4:9- (4-aminophenyl) -9H-carbazole-3, 6-diamine
Figure BDA0003864948300000085
IM-5:4- [ bis (4-aminophenyl) -4H-1,2, 4-triazol-3-yl ] aniline
Figure BDA0003864948300000086
IM-6：
Figure BDA0003864948300000091
Synthesis example 1:
120.00g of NMP and 12.51g of IM-1 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, then 61.26g (0.3 mol) of AD-1 was slowly added, after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and the reaction was carried out at 35 ℃ for 3 hours after completion of the dropwise addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-1.
Figure BDA0003864948300000092
The structural formula of the obtained cross-linking agent PM-1 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears at 1640cm -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 2:
120.00g of NMP and 12.61g of IM-2 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, then 61.26g (0.3 mol) of AD-1 was slowly added, after completion of the addition, the reaction mixture was allowed to stand at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and the reaction mixture was reacted at 35 ℃ for 3 hours after completion of the dropwise addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And washing the mixture for three times by using deionized water after filtration, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-2.
Figure BDA0003864948300000093
The structural formula of the obtained cross-linking agent PM-2 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 3:
under the protection of nitrogen, 120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 61.26g (0.3 mol) of AD-1 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And washing the mixture for three times by using deionized water after filtration, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-3.
Figure BDA0003864948300000101
The structural formula of the obtained cross-linking agent PM-3 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 4:
under the protection of nitrogen, 120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 61.26g (0.3 mol) of AD-1 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-4.
Figure BDA0003864948300000102
The structural formula of the obtained cross-linking agent PM-4 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears at 1640cm -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 5:
120.00g of NMP and 34.24g of IM-5 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, then 61.26g (0.3 mol) of AD-1 was slowly added, after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of a solution prepared from N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and the reaction was carried out at 35 ℃ for 3 hours after completion of the dropwise addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-5.
Figure BDA0003864948300000111
The structural formula of the obtained cross-linking agent PM-5 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 6:
120.00g of NMP and 12.51g (0.1 mol) of IM-1 were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, and stirred to dissolve them, 42.04g (0.3 mol) of AD-2 was slowly added thereto, and after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and then the reaction was carried out at 35 ℃ for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And washing the mixture for three times by using deionized water after filtration, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-6.
Figure BDA0003864948300000112
The structural formula of the obtained cross-linking agent PM-6 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can be provedThe synthesis of the cross-linking agent is clearly successful.
Synthesis example 7:
120.00g of NMP and 12.61g (0.1 mol) of IM-2 were added to a 500mL three-necked flask equipped with a stirrer and a thermometer in this order under nitrogen atmosphere, and stirred and dissolved, and then 42.04g (0.3 mol) of AD-2 was slowly added thereto, and after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, and after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and then the reaction was carried out at 35 ℃ for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-7.
Figure BDA0003864948300000113
The structural formula of the obtained cross-linking agent PM-7 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 8:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 were added to a 500mL three-necked flask equipped with a stirrer and a thermometer in this order under nitrogen atmosphere, and stirred to dissolve them, 42.04g (0.3 mol) of AD-2 was slowly added thereto, and after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and then the reaction was carried out at 35 ℃ for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-8.
Figure BDA0003864948300000121
The structural formula of the obtained cross-linking agent PM-8 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 9:
120.00g of NMP and 28.84g (0.1 mol) of IM-4 were added to a 500mL three-necked flask equipped with a stirrer and a thermometer in this order under nitrogen atmosphere, and stirred to dissolve them, 42.04g (0.3 mol) of AD-2 was slowly added thereto, and after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and then the reaction was carried out at 35 ℃ for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-9.
Figure BDA0003864948300000122
The structural formula of the obtained cross-linking agent PM-9 is shown as above, and the cross-linking agent is subjected to infrared light according to the detection methodSpectrum test, spectrum display, 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 10:
under the protection of nitrogen, 120.00g of NMP and 34.24g (0.1 mol) of IM-5 are added into a 500mL three-neck flask with a stirrer and a thermometer in sequence, stirred and dissolved, 42.04g (0.3 mol) of AD-2 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added, and the reaction is carried out at 35 ℃ for 3h after the addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-10.
Figure BDA0003864948300000131
The structural formula of the obtained cross-linking agent PM-10 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 With C-O bonds representing C-C (= O) -OThe stretching vibration absorption peak, the above information can prove the successful synthesis of the cross-linking agent.
Synthesis example 11:
under the protection of nitrogen, 120.00g of NMP and 12.51g of IM-1 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-11.
Figure BDA0003864948300000132
The structural formula of the obtained cross-linking agent PM-11 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 A stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 12:
under the protection of nitrogen, 120.00g of NMP and 12.61g of IM-2 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-12.
Figure BDA0003864948300000141
The structural formula of the obtained cross-linking agent PM-12 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 13:
under the protection of nitrogen, 120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-13.
Figure BDA0003864948300000142
The structural formula of the obtained cross-linking agent PM-13 is shown as above,the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrum shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 14:
under the protection of nitrogen, 120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-14.
Figure BDA0003864948300000151
The structural formula of the obtained cross-linking agent PM-14 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 15:
under the protection of nitrogen, 120.00g of NMP and 34.24g of IM-5 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-15.
Figure BDA0003864948300000152
The structural formula of the obtained cross-linking agent PM-15 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 An expansion and contraction vibration absorption peak of C = O bond of C-C (= O) -O, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 16:
under the protection of nitrogen, 120.00g of NMP and 12.51g of IM-1 (0.1 mol) are sequentially added into a 500mL three-necked flask with a stirrer and a thermometer and stirred to dissolve, 55.85g (0.3 mol) of AD-4 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added, and the reaction is carried out at 35 ℃ for 3h after the addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-16.
Figure BDA0003864948300000161
The structural formula of the obtained cross-linking agent PM-16 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears at 1640cm -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 A stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 17:
120.00g of NMP and 12.61g of IM-2 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, 55.85g (0.3 mol) of AD-4 was slowly added thereto, and after completion of the addition, reacted at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of a solution prepared from N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise thereto, and reacted at 35 ℃ for 3 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-17.
Figure BDA0003864948300000162
The structural formula of the obtained cross-linking agent PM-17 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears at 1640cm -1 ～1660cm -1 The vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 A stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 18:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, 55.85g (0.3 mol) of AD-4 was slowly added, after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 53.62g (0.45 mol) of N, N-dimethylformamide dimethylacetal diluted with 50.00g of NMP was added dropwise, and the reaction was carried out at 35 ℃ for 3 hours after completion of the dropwise addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-18.
Figure BDA0003864948300000171
The structural formula of the obtained cross-linking agent PM-18 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears at 1640cm -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 The occurrence of C-C (= O) -OC = O bond absorption peak of stretching vibration, 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 19:
under the protection of nitrogen, 120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 55.85g (0.3 mol) of AD-4 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-19.
Figure BDA0003864948300000172
The structural formula of the obtained cross-linking agent PM-19 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 20:
under the protection of nitrogen, 120.00g of NMP and 34.24g of IM-5 (0.1 mol) are sequentially added into a 500mL three-necked flask provided with a stirrer and a thermometer and stirred to be dissolved, 55.85g (0.3 mol) of AD-4 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added dropwise, and the reaction is carried out at 35 ℃ for 3h after the dropwise addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-20.
Figure BDA0003864948300000181
The structural formula of the obtained cross-linking agent PM-20 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 A stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 21
Under the protection of nitrogen, 120.00g of NMP and 42.35g of IM-6 (0.1 mol) are sequentially added into a 500mL three-necked flask with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction solution is cooled to 35 ℃, 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is added, and the reaction is carried out at 35 ℃ for 3h after the addition is completed. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-21.
Figure BDA0003864948300000182
The structural formula of the obtained cross-linking agent PM-21 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 At the position where the absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of-NH 2 disappears at 1640cm -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 The stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove the successful synthesis of the crosslinking agent.
Synthesis example 22:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) were added in this order to a 500mL three-necked flask equipped with a stirrer and a thermometer under nitrogen atmosphere, stirred and dissolved, 51.64g (0.3 mol) of AD-3 was slowly added thereto, after completion of the addition, the reaction was carried out at 80 ℃ for 10 hours, after completion of the reaction, the reaction mixture was cooled to 35 ℃ and 66.25g (0.45 mol) of N, N-dimethylformamide diethylacetal diluted with 50.00g of NMP was added dropwise thereto, and the reaction was carried out at 35 ℃ for 3 hours after completion of the dropwise addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-22.
Figure BDA0003864948300000191
The structural formula of the obtained cross-linking agent PM-22 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 Absorption peak of asymmetric stretching vibration and symmetric stretching vibration of 1640cm disappears -1 ～1660cm -1 Vibration absorption peak at C = O bond of-CONH, 1540cm -1 ～ 1550cm -1 Vibration absorption peak at C-N bond of-CONH, 1730cm -1 ～1740cm -1 A stretching vibration absorption peak of C = O bond of C-C (= O) -O was observed at 1210cm -1 ～1165cm -1 A stretching vibration absorption peak of the C-O bond of C-C (= O) -O appears, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 23:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 61.26g (0.3 mol) of AD-1 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction liquid is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is then added into the reaction system, after the uniform stirring, 61.26g (0.6 mol) of acetic anhydride is slowly added, and the reaction is carried out at 25 ℃ for 20h. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-23.
Figure BDA0003864948300000192
The structural formula of the obtained cross-linking agent PM-23 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration disappears, and the peak is 1780cm -1 The absorption peak of antisymmetric stretching vibration of imide ring C = O appears on the left and right, 1380cm -1 The flexible vibration absorption peak of the C-O bond of the imide ring appears nearby, and the information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 24:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask with a stirrer and a thermometer, stirred and dissolved, 42.04g (0.3 mol) of AD-2 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10 hours, after the reaction is completed, the reaction liquid is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is then added into the reaction system, after uniform stirring, 61.26g (0.6 mol) of acetic anhydride is slowly added, and the reaction is carried out at 25 ℃ for 20 hours. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-24.
Figure BDA0003864948300000201
The structural formula of the obtained cross-linking agent PM-24 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration disappears, and the peak is 1780cm -1 The absorption peak of antisymmetric stretching vibration of imide ring C = O appears on the left and right, 1380cm -1 The flexible vibration absorption peak of the C-O bond of the imide ring appears nearby, and the information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 25:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer and stirred to be dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction liquid is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is then added into the reaction system, after the uniform stirring, 61.26g (0.6 mol) of acetic anhydride is slowly added, and the reaction is carried out at 25 ℃ for 20h. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-25.
Figure BDA0003864948300000202
The structural formula of the obtained cross-linking agent PM-25 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration disappears, and the peak is 1780cm -1 The opposite symmetry of imide ring C = O appears on the left and rightAbsorption peak of telescopic vibration of 1380cm -1 The flexible vibration absorption peak of the imide ring C-O bond appears nearby, and the information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 26:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 55.85g (0.3 mol) of AD-4 is slowly added, after the addition is completed, the reaction is carried out at 80 ℃ for 10h, after the reaction is completed, the reaction liquid is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is then added into the reaction system, after uniform stirring, 61.26g (0.6 mol) of acetic anhydride is slowly added, and the reaction is carried out at 25 ℃ for 20h. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-26.
Figure BDA0003864948300000203
The structural formula of the obtained cross-linking agent PM-26 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration disappears, and the peak is 1780cm -1 The absorption peak of antisymmetric stretching vibration of imide ring C = O appears on the left and right, 1380cm -1 The flexible vibration absorption peak of the imide ring C-O bond appears nearby, and the information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 27:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 61.26g (0.3 mol) of AD-1 is slowly added, after the materials are added, the reaction is carried out for 10 hours at 80 ℃, after the reaction is finished, the reaction liquid is cooled to 25 ℃, and the reaction liquid is poured into 3L of deionized water, so that white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-27.
Figure BDA0003864948300000211
The structural formula of the obtained cross-linking agent PM-27 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (1) disappears at 1710cm -1 The stretching vibration absorption peak of the C = O bond of-COOH appears on the left and right, and the above information can prove the successful synthesis of the cross-linking agent.
Synthesis example 28:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 42.04g (0.3 mol) of AD-2 is slowly added, after the materials are added, the reaction is carried out for 10 hours at 80 ℃, after the reaction is finished, the reaction liquid is cooled to 25 ℃, and the reaction liquid is poured into 3L of deionized water, so that white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-28.
Figure BDA0003864948300000212
The structural formula of the obtained cross-linking agent PM-28 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (1) disappears at 1710cm -1 The stretching vibration absorption peak of the C = O bond of-COOH appears on the left and right, and the above information can prove the successful synthesis of the cross-linking agent.
Synthesis example 29:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 51.64g (0.3 mol) of AD-3 is slowly added, after the materials are added, the reaction is carried out for 10 hours at 80 ℃, after the reaction is finished, the reaction liquid is cooled to 25 ℃, and the reaction liquid is poured into 3L of deionized water, so that white precipitate is separated out. And after filtration, washing the mixture with deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-29.
Figure BDA0003864948300000221
The structural formula of the obtained cross-linking agent PM-29 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrum shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (1) disappears at 1710cm -1 The stretching vibration absorption peak of the C = O bond of-COOH appears on the left and right, and the above information can prove that the cross-linking agent is successfully synthesized.
Synthesis example 30:
under the protection of nitrogen, 120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask provided with a stirrer and a thermometer, stirred and dissolved, 55.85g (0.3 mol) of AD-4 is slowly added, after the materials are added, the reaction is carried out for 10 hours at 80 ℃, after the reaction is finished, the reaction liquid is cooled to 25 ℃, and the reaction liquid is poured into 3L of deionized water, so that white precipitate is separated out. And after filtration, washing the mixture by using deionized water for three times, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the cross-linking agent PM-30.
Figure BDA0003864948300000222
The structural formula of the obtained cross-linking agent PM-30 is shown as above, infrared spectrum test is carried out on the cross-linking agent according to the detection method, and the spectrogram shows that 3400cm -1 ～3500cm -1 To NH of 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (1) disappears at 1710cm -1 The stretching vibration absorption peak of C = O bond of-COOH appears on the left and right, and the information can prove that the cross-linking agent is successfully synthesized
In the present invention, BANI-M (pill petrochemicals) having the following structure was compared with the crosslinking agent of the present invention:
Figure BDA0003864948300000223
the solubility of the crosslinking agent synthesized in the synthesis example was measured according to the above-mentioned method for measuring the solubility of the crosslinking agent, and the results are shown in Table 1.
It can be seen from Table 1 that the tri-functional N-heterocycle-containing crosslinking agents having an amic acid ester structure synthesized in Synthesis examples 3, 8, 13 and 18 have a solubility in GBL, EL and PGME which is much higher than that of the crosslinking agents having an imide structure synthesized in Synthesis examples 22 to 23, and are also higher than that of BANI-M, a PETROL-based crosslinking agent. The imide-structured cross-linking agent is substantially insoluble in PGME, severely limiting its applications.
It can be seen from table 1 that the storage stability of the trifunctional N-heterocycle-containing crosslinking agents having an amic acid ester structure synthesized in synthesis examples 3, 8, 13 and 18 is much higher than that of the crosslinking agents having an amic acid structure synthesized in synthesis examples 26 to 29, because amic acid is very likely to undergo hydrolysis side reactions, and is particularly disadvantageous in high-temperature and high-humidity environments for the application and storage of the product.
From the above results, it can be seen that the performance of the N-heterocycle containing trifunctional crosslinking agent of the amic acid esters synthesized by the present invention is optimal. According to different application scenes, the N-heterocycle-containing tri-functionality cross-linking agent of the amic acid esters with different structures and the proper optimal dosage thereof can be selected.
TABLE 1 crosslinker purity and solubility test results
Figure BDA0003864948300000231
Preparation of photosensitive resin composition
Example 1
31.02g (0.1 mol) of ODPA and 100.00g of NMP were sequentially charged into a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and dissolved by stirring at room temperature to obtain a dianhydride solution. In another three-necked flask equipped with a stirrer, 54.41g (0.09 mol) of HFHA and 100.00g of NMP were added in this order and dissolved by stirring to obtain a diamine solution. And dropwise adding a diamine solution into the dianhydride solution, reacting at normal temperature for 1h after dropwise adding is finished, and then reacting at 50 ℃ for 2h. After completion of the reaction, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethyl acetal diluted with 45.00g of NMP was added dropwise thereto, and the reaction was carried out at 50 ℃ for 3 hours after completion of the addition. After the reaction was completed, the reaction solution was poured into 3L of deionized water to precipitate a polymer and obtain a white precipitate. And washing the mixture for three times by using deionized water after filtration, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the polyamide acid ester P-1.
10.00g of synthesized polyamic acid ester P-1, 1.00g of crosslinking agent PM-1, 2.00g of NT-300 (manufactured by Toyo Synthesis industries, japan), 1.00g of GBL, 20.00g of EL and 70.00g of PGME are sequentially added into a three-necked flask with stirring and dissolved, after clarification, 0.20g of gamma-glycidyl ether oxypropyl trimethoxysilane (Nanjing Dimont, KH-560), 0.15g of flatting agent BYK-392 and 0.15g of defoaming agent BYK-A530 are added, and after stirring is continued uniformly, the mixture is filtered by a 1-micron PP filter membrane to obtain the photosensitive resin composition.
Example 2
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-2.
Example 3
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-3.
Example 4
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-4.
Example 5
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-5.
Example 6
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-6.
Example 7
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-7.
Example 8
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-8.
Example 9
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-9.
Example 10
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-10.
Example 11
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-11.
Example 12
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-12.
Example 13
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-13.
Example 14
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-14.
Example 15
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-15.
Example 16
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-16.
Example 17
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-17.
Example 18
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-18.
Example 19
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-19.
Example 20
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-20.
Example 21
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-21.
Example 22
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-22.
Example 23
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 0.50g of the crosslinking agent PM-13.
Example 24
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 2.00g of the crosslinking agent PM-13.
Example 25
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 0.10g of the crosslinking agent PM-13.
Example 26
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 4.00g of the crosslinking agent PM-13.
Example 27
31.02g (0.1 mol) of ODPA and 100.00g of NMP were sequentially charged into a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and dissolved by stirring at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, and 32.96g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) and 100.00g of NMP were sequentially added thereto and dissolved by stirring to obtain a diamine solution. And dropwise adding a diamine solution into the dianhydride solution, reacting at normal temperature for 1h after dropwise adding is finished, and then reacting at 50 ℃ for 2h. After completion of the reaction, a solution of 23.83g (0.2 mol) of N, N-dimethylformamide dimethylacetal diluted with 45.00g of NMP was added dropwise thereto, and the reaction was carried out at 50 ℃ for 3 hours after completion of the addition. After the reaction was completed, the reaction solution was poured into 3L of deionized water to precipitate a polymer and obtain a white precipitate. And washing the mixture for three times by using deionized water after filtration, putting the mixture into a vacuum oven, and drying the mixture for 72 hours at the temperature of 80 ℃ to obtain the polyamide acid ester P-2.
A three-necked flask equipped with a stirrer was charged with 10.00g of the synthesized polyamic acid ester P-2, 1.00g of the crosslinking agent PM-13, 2.00g of NT-300 (manufactured by Toyo Synthesis industries, ltd., japan), 1.00g of GBL, 20.00g of EL and 70.00g of PGME in this order, and after the mixture was dissolved by stirring, 0.20g of KH-560,0.15g of BYK-392 and 0.15g of BYK-A530 were added thereto and after the mixture was clarified, the mixture was further stirred uniformly and filtered through a 1 μm filter PP to obtain a photosensitive resin composition.
Example 28
Example 26 was repeated, except that 1.00g of the crosslinking agent PM-13 was replaced with 1.00g of the crosslinking agent PM-18.
Example 29
31.02g (0.1 mol) of ODPA was placed in a 500mL three-necked flask, 26.03g (0.2 mol) of hydroxyethyl methacrylate (HEMA) and 100.00g of GBL were added thereto, and 15.82g of pyridine (0.2 mol) was added dropwise with stirring at 10 ℃ or lower to obtain a reaction mixture, which was allowed to naturally rise to 25 ℃ and then stirred for 12 hours.
Next, this reaction mixture was stirred for 40 minutes while adding 41.25g (0.2 mol) of Dicyclohexylcarbodiimide (DCC) dissolved in 50.00g of GBL solution under ice-bath conditions, 19.03g (0.095 mol) of 4,4' -diaminodiphenyl ether (ODA) dissolved in 70.00g of GBL solution was added under nitrogen protection over 60 minutes, the temperature was naturally raised to 25 ℃ and 80.00g of GBL was added, stirring was continued for 12 hours, then 6.00g of ethanol was added and stirred for 1 hour, and the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 1L of ethanol to precipitate a polymer, the precipitated polymer was dissolved in 300mL of tetrahydrofuran, the obtained polymer solution was dropped into 5L of ultrapure water to precipitate a polymer precipitate, the obtained precipitate was filtered off, and vacuum drying was performed at 50 ℃ for 72 hours to obtain polyamic acid ester P-3.
10.00g of the synthesized polymer P-3 was dissolved in 20.00g of NMP in a three-necked flask equipped with a stirrer, and after completely dissolving the polymer P-3, 1.00g of a crosslinking agent PM-13, 1.00g of 3- (triethoxysilylthio) propyltrimethoxysilane (Nippon Becheng chemical, X-12-1056 ES) and 0.20g of KH-560 were added thereto, followed by stirring until completely dissolving the polymer P-3, and then 0.30g of a photoinitiator 1- (4-phenylthio-phenyl) -octyl-1, 2-dione-2-oxime-0-benzoate (OXE-1, BASF), 1.50g of a crosslinking agent tetraethyleneglycol dimethacrylate (TEGDMA) and 0.10g of a polymerization inhibitor P-hydroxyanisole (MEHQ) were sequentially added thereto, and after sufficiently dissolving the polymer P-3 and the mixture was subjected to filter pressing with a filter to obtain a photosensitive resin composition.
Example 30
Example 28 was repeated, except that 1.00g of the crosslinking agent PM-13 was replaced with 1.00g of the crosslinking agent PM-18.
Comparative example 1
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-23.
Comparative example 2
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-24.
Comparative example 3
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-25.
Comparative example 4
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-26.
Comparative example 5
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-27.
Comparative example 6
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-28.
Comparative example 7
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-29.
Comparative example 8
Example 1 was repeated, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent PM-30.
Comparative example 9
Example 1 was followed, except that 1.00g of the crosslinking agent PM-1 was replaced with 1.00g of the crosslinking agent BANI-M.
Comparative example 10
Example 1 was repeated except that 1.00g of the crosslinking agent PM-1 was replaced with 2, 6-dimethoxymethylene-4-tert-butylphenol (DMOM-PTBP-MF, chemical of the State).
Comparative example 11
The same procedure as in example 1 was repeated, except that no crosslinking agent was added to the system.
The photosensitive resin compositions of examples and comparative examples were characterized according to the above-mentioned film-forming property, imidization ratio, glass transition temperature, tensile strength, and dielectric constant test methods, and the specific results are shown in Table 2.
As can be seen from table 2: as can be seen from comparison of examples 1 to 21 with comparative examples 9 to 11, the cured films containing the N-heterocyclic ring of the present invention exhibited higher imidization rate, which is significantly better than that of the pellet-type petrochemical crosslinking agent, other types of crosslinking agents, or no crosslinking agent. As can be seen from comparison among examples 3, 8, 13, and 18 and comparative examples 1 to 4, the crosslinking agent having an amic acid ester structure exhibits better effects of increasing imidization rate, glass transition temperature, and tensile strength than the imide structure because of its better compatibility with polymers and higher solubility in GBL, EL, and PGME, while the crosslinking agent having an imide structure does not function in the composition system due to its poor solubility, and the cured film obtained therefrom has poor properties. Comparing examples 1 to 21 with comparative examples 9 to 11, it can be seen that the crosslinking agent containing N heterocycle of the present invention has a great accelerating effect on the film forming property of the cured film compared to other crosslinking agents or no crosslinking agent is added, and has an excellent film forming property at a curing temperature of 250 ℃ at a low temperature, indicating that the N heteroatom in the crosslinking agent has an accelerating effect on imidization. In comparison between examples 13 and 22 to 25, it is seen that when the amount of the crosslinking agent added is too small, the advantageous effect of the cured film is not significant, and when the amount of the crosslinking agent added is too large, although the imidization rate and the glass transition temperature are high, the film is relatively brittle and poor in film forming property, so that the amount of the crosslinking agent added is preferably 5 to 20% by mass based on the mass of the resin. Examples 3, 8, 13, and 18 and comparative examples 5 to 8 show that a crosslinking agent having an amic acid structure also exhibits excellent film properties, but is not preferred because of its poor storage stability. In addition, it can be seen from examples 1 to 21 and comparative examples 9 to 11 that the cured compositions with the N-containing heterocyclic cross-linking agent of the present invention exhibit lower dielectric constants and can be well applied to passivation insulating layers of OLED devices.
TABLE 2 cured film Performance test results of the photosensitive resin compositions
Figure BDA0003864948300000261
Figure BDA0003864948300000271
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. A trifunctional crosslinking agent, wherein the trifunctional crosslinking agent has a structure of formula i:
Figure FDA0003864948290000011
wherein W is an organic group containing an N-heterocycle;
X 1 、X 2 、X 3 are respectively and independently selected from any one of the structures shown in general formulas II to IV
Figure FDA0003864948290000012
In the general formulas II to IV:
R 1 is a C1E20 alkyl or alkoxy;
R 2 、R 3 is hydrogen atom or organic group with 1-6 carbon atoms;
R 4 is an alkynyl-containing organic group.
2. The trifunctional crosslinking agent according to claim 1, wherein W is an organic group having 2 to 40 carbon atoms;
R 4 selected from alkynyl-containing organic groups having 2 to 20 carbon atoms.
3. The trifunctional crosslinking agent of claim 1, wherein the N-heterocycle is selected from one of triazine, triazole, pyridine, carbazole, pyrimidine, imidazole, benzothiazole;
preferably, R 1 One selected from methyl, ethyl, propyl, n-butyl, tert-butyl and hydroxyethyl methacrylate;
preferably, R 4 Is selected from
Figure FDA0003864948290000013
One kind of (1).
4. The trifunctional crosslinking agent of claim 1, wherein W is selected from the following structural formula:
Figure FDA0003864948290000021
5. a method for preparing a trifunctional cross-linking agent, comprising the steps of:
s1, reacting a mixture containing anhydride, an N heterocyclic compound and an organic solvent to obtain a precursor liquid;
and S2, adding an esterification reagent into the precursor liquid, and reacting II to obtain the tri-functionality cross-linking agent.
6. The method according to claim 5, wherein in step S1, the acid anhydride is selected from any one of the following structures:
Figure FDA0003864948290000022
wherein R is 2 、R 3 、R 4 The same as in claim 1;
preferably, in step S1, the N-heterocyclic compound is selected from compounds represented by the following structures:
Figure FDA0003864948290000031
preferably, in step S1, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone, γ -butyrolactone, tetrahydrofuran, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether;
preferably, in step S1, the molar ratio of the acid anhydride to the N-heterocyclic compound is 3:0.9 to 1.1;
preferably, in step S1, the mass ratio of the acid anhydride to the organic solvent is 5 to 50:100, respectively;
preferably, in step S1, the conditions of reaction I are as follows:
the temperature is 10-150 ℃;
the time is 3-24 h.
7. The method according to claim 5, wherein in step S2, the esterification reagent is selected from at least one of N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dineopentylbutyl acetal, N-dimethylformamide di-tert-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4- (4, 6-dimethoxy-1, 3, 5-triazin-2-yl) -4-methylmorpholine 28355hydrochloride, hydroxyethyl methacrylate, 4-nitrobenzyl alcohol;
preferably, the molar ratio of the addition amount of the esterification reagent in step S2 to the addition amount of the acid anhydride in step S1 is 1 to 5:1;
preferably, in step S2, the conditions of reaction ii are as follows:
the temperature is 20-80 ℃;
the time is 2-24 h.
8. A photosensitive resin composition, comprising the following components:
a component a: at least one of polyamic acid and polyamic acid ester;
and (b) component b: a trifunctional crosslinking agent;
and (b) component c: a photosensitizer;
and (b) a component d: a solvent;
and (e) component: at least one of a silane coupling agent, a leveling agent and a defoaming agent;
the trifunctional crosslinker is selected from the trifunctional crosslinkers set forth in claim 1.
9. The photosensitive resin composition according to claim 8, wherein the mass ratio of component a to component b is 100:0.5 to 30;
preferably, the mass ratio of component a to component b is 100:5 to 20.
10. An OLED device comprising a passivating insulating layer;
the passivation insulating layer is selected from the photosensitive resin composition according to any one of claims 8 to 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108604061A (en) * 2016-03-18 2018-09-28 东丽株式会社 Cured film and positive type photosensitive organic compound
CN110790717A (en) * 2019-10-31 2020-02-14 南京理工大学 Cross-linking agent for bio-based adhesive and preparation method thereof
CN114456205A (en) * 2021-09-28 2022-05-10 波米科技有限公司 Triazole-based silane coupling agent and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108604061A (en) * 2016-03-18 2018-09-28 东丽株式会社 Cured film and positive type photosensitive organic compound
CN110790717A (en) * 2019-10-31 2020-02-14 南京理工大学 Cross-linking agent for bio-based adhesive and preparation method thereof
CN114456205A (en) * 2021-09-28 2022-05-10 波米科技有限公司 Triazole-based silane coupling agent and preparation method and application thereof

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