CN115521243B - Trifunctional crosslinking agent and preparation method and application thereof - Google Patents

Trifunctional crosslinking agent and preparation method and application thereof Download PDF

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CN115521243B
CN115521243B CN202211177020.7A CN202211177020A CN115521243B CN 115521243 B CN115521243 B CN 115521243B CN 202211177020 A CN202211177020 A CN 202211177020A CN 115521243 B CN115521243 B CN 115521243B
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crosslinking agent
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linking agent
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CN115521243A (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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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/50—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/54—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/82—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The application discloses a trifunctional cross-linking agent, a preparation method and application thereof, and belongs to the field of functional polymer materials. A trifunctional crosslinking agent having the structure of formula i:wherein W is an organic group containing an N-heterocycle; x is X 1 、X 2 、X 3 Respectively and independently selected from structures shown in any of general formulas II-IVIn the general formulas II to IV: r is R 1 Is alkyl or alkoxy with 1 to 20 carbon atoms; r is R 2 、R 3 Is a hydrogen atom or an organic group having 1 to 6 carbon atoms; r is R 4 Is an alkynyl-containing organic group. The trifunctional cross-linking agent contains double bond or alkynyl, N heterocyclic group and amic acid ester structure. The crosslinking agent has low dielectric and high heat resistance.

Description

Trifunctional crosslinking agent and preparation method and application thereof
Technical Field
The application relates to a trifunctional cross-linking agent, a preparation method and application thereof, belonging to the field of functional polymer materials.
Background
The flexible display has the characteristics of light weight, thinness and uneasiness, has diversified 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 a market size of $ 160 billion in 2020. The OLED has high luminous efficiency and high contrast, and can be widely applied to the aspects of mobile phones, digital cameras, navigator, business marks and the like.
Polyimide has excellent light transmittance, thermal property and mechanical property, and is widely applied to the fields of electricity, electronics, vehicles, airplanes, semiconductors and the like. The photosensitive polyimide with low-temperature curing can be coated on a glass substrate of an OLED device, and after patterns are drawn, a polyimide film can be newly formed on the surface of the substrate by low-temperature heat treatment, so that passivation effects such as insulation, water insulation, oxygen insulation 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 very strict, such as low curing temperature, low dielectric constant, high heat resistance and the like.
The current research on photosensitive polyimide coating adhesive for OLED device packaging layers mainly comprises the following steps: in patent CN 109153841A, a resin composition prepared by introducing a phenol skeleton having a crosslinkable group and a phenol skeleton having no crosslinkable group to an alkali-resistant resin can give a cured film excellent in chemical resistance, low stress and high elongation under low-temperature curing conditions. The CN 108779251A patent uses an alkali-soluble resin having a benzoxazole precursor structure and an aliphatic group, a thermal acid generator, and an antioxidant to prepare a cured film capable of being cured at low temperature treatment while having excellent heat resistance, chemical resistance, and elongation at break, and is useful for an insulating layer of an organic electroluminescent element. In addition, soluble polyimide or polyisoimide can be prepared to realize low-temperature curing of the resin, but the resin is often poor in solubility and limited in application. In CN 102047178B, a commercial thermal crosslinking agent made by the company petrochemicals is added to improve the tensile elongation of the cured film and to exhibit good adhesion and lithographic properties, but since this crosslinking agent is imidized, it causes poor solubility in solvents with low solubility such as EL and PGME, which are essential for improving the uniformity of the cured film. In addition, the crosslinking agent of the petroleum pill contains only 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 cross-linking agent having a cross-linkable double bond or alkyne group in its structure which cross-links during curing of the composition to improve film formation and increase glass transition temperature. Meanwhile, the cross-linking agent contains an N heterocyclic group, and nitrogen atoms in the N heterocyclic group can be combined with hydrogen ions to form a complex, so that the dehydration cyclization reaction of polyamide acid or polyamide acid ester can be promoted, and the curing temperature of the composition can be further reduced. The cross-linking agent contains amic acid ester structure, has high compatibility with heat-resistant resins such as polyamic acid and polyamic acid ester, and has better solubility in solvents than cross-linking agents with imide structures, especially gamma-butyrolactone, ethyl lactate, propylene glycol methyl ether and the like.
A trifunctional crosslinking agent having the structure of formula i:
Wherein W is an organic group containing an N-heterocycle;
X 1 、X 2 、X 3 each of which is independently selected from any one of structures shown in general formulas II to IV;
in the general formulas II to IV:
R 1 is alkyl or alkoxy with 1 to 20 carbon atoms;
R 2 、R 3 is a hydrogen atom or an organic group having 1 to 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 Is of the same structure.
Optionally, W is an organic group having 2 to 40 carbon atoms;
R 4 an alkynyl-containing organic group having 2 to 20 carbon atoms;
R 4 selected from alkyl groups having 2 to 10 carbon atoms, alkoxy groups having 2 to 10 carbon atoms, and phenyl groups having 2 to 20 carbon atoms.
Optionally, the N-heterocycle is selected from one of triazine, triazole, pyridine, carbazole, pyrimidine, imidazole, benzothiazole.
Alternatively, R 1 One selected from methyl, ethyl, propyl, n-butyl, tert-butyl and hydroxyethyl methacrylate.
Alternatively, R 4 Selected from the group consisting ofOne of them. Alternatively, W is selected from the following formulae:
according to a second aspect of the present application, there is provided a method of preparing a trifunctional cross-linking agent.
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 precursor liquid;
S2, adding an esterification reagent into the precursor liquid, and reacting II to obtain the trifunctional cross-linking agent.
Optionally, in step S1, the anhydride is selected from any one of the following structures:
wherein R is 2 、R 3 、R 4 R is as described above 2 、R 3 、R 4 Is not limited in terms of the range of (a).
Alternatively, the anhydride contains a double bond or an alkynyl group.
Alternatively, the anhydride containing a double bond is 5-allyl nadic anhydride and allyl succinic anhydride.
Alternatively, the anhydride containing alkynyl groups is 4-ethynyl phthalic anhydride, methyl ethynyl phthalic anhydride.
Optionally, in step S1, the N heterocyclic compound is selected from compounds represented by the following structures:
optionally, 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, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether.
Optionally, 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: any value in 1.10 or a range value between any two.
Optionally, in step S1, the mass ratio of the anhydride to the organic solvent is 5-50: 100.
optionally, in step S1, the mass ratio of the 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: 100. 50:100 or a range of values therebetween.
Alternatively, in step S1, the conditions for reaction I are as follows:
the temperature is 10-150 ℃;
the time is 3-24 hours.
Alternatively, 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 ℃.
Alternatively, the time is independently selected from any value or range of values between any two of 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h.
Optionally, in step S2, the esterifying reagent is selected from at least one of N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dimethylformamide dipropyl acetal, N-dimethylformamide dineopentyl butyl 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 hydrochloride, 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 value between any two.
Alternatively, in step S2, the conditions for reaction ii are as follows:
the temperature is 20-80 ℃;
the time is 2-24 hours.
Alternatively, the temperature is independently selected from any value or range of values between any two of 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃.
Alternatively, the time is independently selected from any value or range of values between any two of 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h.
In another aspect, the invention provides a method for preparing an N-heterocycle containing trifunctional crosslinking agent, comprising the steps of:
SP1: a certain amount of N-containing heterocyclic triamine is weighed and dissolved into a certain amount of solvent.
SP2: adding a certain amount of double bond or alkynyl-containing anhydride into the 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 hours at 20-80 ℃.
SP4: after the reaction is completed, the reaction solution is poured into deionized water, and the cross-linking agent precipitate is obtained through precipitation. And (3) precipitating and filtering the crosslinking agent, washing the crosslinking agent with deionized water for three times, and drying the crosslinking agent for 36 to 120 hours at the temperature of 40 to 100 ℃ under vacuum condition to obtain the N-heterocycle-containing tri-functionality crosslinking agent.
Further, the reaction temperature of SP2 is preferably 50℃to 120℃and more preferably 70℃to 90 ℃.
Further, the reaction temperature of SP4 is preferably 25℃to 50℃and both the esterification efficiency and the imidization side reaction are preferably 30℃to 40 ℃.
Furthermore, the trifunctional crosslinking agent containing N heterocycle contains double bond or alkynyl, which can generate thermal crosslinking reaction under a certain temperature condition, and can be matched with a catalyst for improving the crosslinking effect or reducing the crosslinking temperature. The cross-linking agent contains a cross-linkable functional group, the main body is of an N-heterocycle structure, and the presence of nitrogen atoms on the N-heterocycle can enhance the functionality of the cross-linking agent. In addition, the cross-linking agent has an amic acid ester structure, better stability than the cross-linking agent with an amidic acid structure, better solubility than imide and wider application range. The trifunctional cross-linking agent containing N heterocycle can be used as an additive in materials with polymers such as polyamide acid, polyamide acid ester, polyimide, polybenzoxazole precursor, polybenzoxazole, polyamide, polybenzimidazole, polybenzothiazole, phenolic resin, polyacrylate and the like as a subject structure, can also show different functional characteristics in different polymer materials, and can also be used for adjusting the addition amount or compounding with other catalysts and additives of different types according to different application fields and application requirements.
According to a third aspect of the present application, there is provided a photosensitive resin composition.
A photosensitive resin composition comprising the following components:
component a: at least one of polyamic acid and polyamic acid ester;
component b: a trifunctional crosslinking agent;
component c: a sensitizer;
component d: a solvent;
component e: at least one of a silane coupling agent, a leveling agent and a defoaming agent;
the trifunctional crosslinking agent is selected from the trifunctional crosslinking agents 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, adding the component e, uniformly mixing to obtain a polymer solution with certain viscosity, filtering the polymer solution by 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 or polyimide acid ester structure shown in the general formula (8):
further, in the general formula (8), X 1 An organic group having 4-valence and having 4 to 40 carbon atoms; y is Y 1 An organic group having 2 valences and having 2 to 40 carbon atoms; r is R 5 And R is 6 Each independently represents a hydrogen atom or a saturated aliphatic group having 1 to 10 carbon atoms, or an unsaturated aliphatic group; n represents an integer of 2 to 200.
Further component a is obtained by reacting dianhydride monomer, diamine monomer and esterification reagent.
Further, the dianhydride monomer may be selected from 4,4 '-oxydiphthalic anhydride, 2,3', 4 '-diphenyl ether tetracarboxylic dianhydride, 3',4 '-biphenyl tetracarboxylic dianhydride, 2,3', 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, 2',3,3 '-benzophenone tetracarboxylic dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, bisphenol A type diether dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4' - (hexafluoroisopropenyl) isophthalic anhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride.
Further, the diamine monomer may be selected from: 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -diaminodiphenyl ether 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 4 '-diamino-2, 2' -dimethylbiphenyl, biphenyldiamine, p-phenylenediamine 3,3 '-dihydroxybenzidine, 2' -bis (3-amino-4-hydroxyphenyl) propane, 2 '-bis (3-amino-4-hydroxyphenyl) diphenyl sulfone, 2-bis [ 4-hydroxy-3- (3-amino) benzamide ] hexafluoropropane 2,2' -bis (trifluoromethyl) - (1, 1 '-diphenyl) 4,4' -diamine, 9-bis (4-aminophenyl) fluorene, 2-bis (4- (4-aminophenoxyphenyl)) propane, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane 3,3 '-bis (2, 3,5, 6-tetrafluoro-4-vinylphenoxy) -4,4' -biphenyldiamine, 2 '-bis [4- (2, 3,5, 6-tetrafluoro-4-vinylphenoxy) -3-aminophenyl ] hexafluoropropane, 2' -bis [4- (2, 3,5, 6-tetrafluoro-4-vinylphenoxy) -3-aminophenyl ] propane, 1, 3-bis (1-amino-3-trifluoromethylphenoxy) -5- (2, 3,5, 6-tetrafluoro-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 and shown in structural formulas I-IV, and the mass ratio of the component a to the component b is 100:0.5 to 30 percent;
preferably, the mass ratio of the component a to the component b is 100: 5-20;
further, component c is a sensitizer, and the sensitizer c varies depending on the component a of the photosensitive resin composition of the present invention.
First, a negative type will be described. In this case, a photopolymerization initiator is preferably a photo radical polymer initiator, and for example, an acetophenone compound, a biimidazole compound, a triazine compound, an oxime compound, or a mixture of 2 or more kinds may be used. The photopolymerization initiator is preferably exemplified by 1- (4-phenylsulfanyl-phenyl) -oct-1, 2-dione-2-oxime-0-benzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, dibenzoyl ketone, 4-benzoyl-4 '-methyldiphenyl ketone, fluorenone, 2' -diethoxyacetophenone, 2-hydroxy-2-methylpropenyl acetone, and 2-epoxy-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylsulfanyl } acetate, but is not limited thereto. The photopolymerization initiator is more preferably an oxime ester, especially from the viewpoint of sensitivity.
Next, a case where the positive form is desired will be described. In this case, as the c-sensitizer, a photoacid generator is used, and specifically, a diazonium quinone compound, an onium salt, a halogen-containing compound, and the like can be used, but from the viewpoints of solvent solubility and storage stability, an ester compound in which quinone diazide sulfonic acid is bonded to a polyhydroxy compound through an ester bond is preferable, and examples of the polyhydroxy compound include: 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. Commercial quinone diazide compounds are preferred, such as NT-300, 4NT-350, 4NT-300, HP-190 (manufactured by Toyo Seisakusho Kogyo Co., ltd.).
Further, the mass ratio of the component a to the component c is 100:0.1 to 30;
preferably, the mass ratio of component a to component c is 100:2 to 25;
further, the solvent of the component d is one or more of aromatic hydrocarbons such as N-methyl-2-pyrrolidone, gamma-butyrolactone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, 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: 70-3000;
preferably, the mass ratio of the component a to the component d is 100: 150-1500.
Further, examples of the silane coupling agent in the component e include gamma-glycidoxypropyl trimethoxysilane, (8-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3- (triethoxysilylthio) propyl trimethoxysilane, 3- (trimethoxysilyl) -1-propanethiol, gamma-thiopropyl triethoxysilane (Nanjiegaku new material technology, KH-580), 3-ureidopropyl triethoxysilane, 3-ureidopropyl trimethoxysilane, 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 organosilicon 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, examples of the defoaming agent include BYK-A530, BYK-A550 and Airex-920 industrial products.
Further, the mass ratio of the component a to the defoamer is 100:0.1 to 10;
further, the photosensitive resin composition may further contain, depending on the application, an additive such as a photoinitiator, a crosslinking agent, a polymerization inhibitor, etc., which 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 compositions described above.
The application has the beneficial effects that:
1) The trifunctional cross-linking agent provided by the application contains an amic acid ester structure, has very high compatibility with heat-resistant resins such as polyamic acid, polyamic acid ester and the like, and has better solubility in solvents than cross-linking agents with imide structures, in particular to solvents such as gamma-butyrolactone, ethyl lactate, propylene glycol methyl ether and the like; the storage stability of the cross-linking agent is better than that of the cross-linking agent with an amic acid structure. The crosslinking agent has low dielectric and high heat resistance.
2) The photosensitive resin composition provided by the application can be used for packaging semiconductor chips, can be used for improving the film forming property of a packaging layer, improving the glass transition temperature and mechanical strength of the packaging layer, and reducing the curing temperature of the packaging layer, so that the reliability and reliability of the chips are greatly improved.
Drawings
Fig. 1 is a cross-sectional view of an OLED device of the present application.
FIG. 2 is an infrared spectrum of the photosensitive resin composition of example 13 at different curing temperatures.
FIG. 3 is a graph showing the change in imidization rate at different curing temperatures.
List of parts and reference numerals:
1-a glass substrate; 2-indium tin oxide; 3-passivating the insulating layer; 4-a light emitting layer; 5-cathode; 6-isolating columns.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analysis method in the embodiment of the application is as follows:
(1) Infrared spectroscopy testing
The synthesized cross-linker samples were tested using a KBr tabletting method using an infrared spectrometer (Shimadzu, IRAfforescence-1S) to determine whether the cross-linker of the present application was successfully prepared.
(2) Cross-linker purity test
The purity of the synthesized cross-linker was tested using a liquid chromatograph (shimadzu, LC-2030). Chromatographic column: c18; wavelength: 254nm; column incubator: 40 ℃; mobile phase: 0.1% phosphoric acid aqueous solution: acetonitrile=40: 60; flow rate: 1.0ml/min.
(3) Cross-linker solubility test
Weighing 100g of gamma-butyrolactone (GBL), ethyl Lactate (EL) or Propylene Glycol Methyl Ether (PGME) in a beaker, placing the beaker in a water bath kettle for constant temperature to 30 ℃, weighing a certain amount of cross-linking agent, placing the weighed cross-linking agent in the solvent, stirring for dissolution, 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 obtain the solubility of the cross-linking agent in the solvent, wherein the unit is 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 heating table (HT-300 laboratory electric plate, guangzhou Grina Instrument Co., ltd.) at 120℃for soft baking for 3 minutes to obtain a resin film having a film thickness of 10 to 20. Mu.m. Then the film is placed in a vacuum anaerobic oven (MOLZK-32D 1) under the protection of nitrogen atmosphere, and after heat treatment for 30 minutes at 170 ℃, the temperature is raised to 250 ℃ for 1 hour, and the film is treated for 1 hour at 250 ℃, and then the film is directly naturally cooled to below 50 ℃ in the oven, and finally the cured film is obtained. And (3) placing the silicon wafer with the solidified film in hydrofluoric acid solution, and carrying out corrosion stripping on the silicon wafer. Film forming properties were evaluated using the following criteria.
"you": the resin composition can form a film, has toughness and is not broken after being folded in half;
"good": the resin composition can form a film, has toughness and is folded and broken;
"difference": the resin composition was unable to form a film and was in the form of chips.
When the film forming property is "excellent", other test evaluation may be further performed.
(5) Imidization test of cured film
Infrared spectra of the cured films at the curing temperatures of 250℃and 350℃were measured by the ATR method using an infrared spectrometer (Shimadzu, IRAfforescence-1S), and 1380cm was recorded -1 Intensity A of the stretching vibration absorption peak of C-N bond and 1500cm -1 Absorption peak intensity a of benzene ring at the position.
The calculation formula of the imidization degree alpha is as follows:
(6) Glass transition temperature test
About 10g of the cured film obtained at 250℃was placed in a standard aluminum container, and the glass transition temperature (Tg) was measured by using a DSC-25 (Watts Co., TA instruments, U.S.A.). The measurement was carried out at a temperature rising rate of 20℃per minute after preliminary drying at 80℃for 1 hour.
(7) Tensile Strength test
The cured film prepared from the photosensitive resin composition was cut into sample bars having a size of 40 mm long and 5 mm wide, and the bars were subjected to a tensile strength test using DMA-850 (Watts Co., TA instruments, USA) at a temperature of 150℃and a tensile force in the range of 0 to 18N at a rate of 3N/min.
(8) Dielectric constant test
A novocorol broadband dielectric and impedance spectrometer (BDS 40 germany) at 25 ℃ with an electrode diameter of 2 cm was used to test the frequency range: 0.1 Hz-100 MHz.
The abbreviations used in the present application are as follows:
NMP: n-methylpyrrolidone
GBL: gamma butyrolactone
EL: lactic acid ethyl ester
PGME: propylene glycol methyl ether
ODPA:4, 4-oxydiphthalic anhydride
HFHA:2, 2-bis [ 4-hydroxy-3- (3-amino) benzamido ] hexafluoropropane
BAHF:2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
ODA:4,4' -diaminodiphenyl ether
AD-1: 5-allyl nadic anhydride
AD-2: allyl succinic anhydride
AD-3: 4-ethynyl phthalic anhydride
AD-4: methyl ethynyl phthalic anhydride
IM-1:2,4, 6-triaminopyrimidines
IM-2:1,3, 5-triazine-2, 4, 6-triamine
IM-3:2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine
IM-4:9- (4-aminophenyl) -9H-carbazole-3, 6-diamine
IM-5:4- [ bis (4-aminophenyl) -4H-1,2, 4-triazol-3-yl ] aniline
IM-6：
Synthesis example 1:
120.00g of NMP and 12.51g of IM-1 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-1.
The structural formula of the obtained cross-linking agent PM-1 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 2:
120.00g of NMP and 12.61g of IM-2 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 is slowly added, after the addition is completed, the reaction is carried out for 10 hours at 80 ℃, after the reaction is completed, the reaction solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is carried out for 3 hours at 35 ℃. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and white precipitate is obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-2.
The structural formula of the obtained cross-linking agent PM-2 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 3:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-3.
The structural formula of the obtained cross-linking agent PM-3 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 4:
120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-4.
The structural formula of the obtained cross-linking agent PM-4 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The occurrence of the stretching vibration absorption peak of C-C (=O) -O C-O bond proves successful synthesis of the crosslinking agent。
Synthesis example 5:
120.00g of NMP and 34.24g of IM-5 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 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 solution is cooled to 35 ℃, and a solution obtained by diluting 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal with 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-5.
The structural formula of the obtained cross-linking agent PM-5 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 6:
120.00g of NMP and 12.51g (0.1 mol) of IM-1 are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-6.
The structural formula of the obtained cross-linking agent PM-6 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 7:
120.00g of NMP and 12.61g (0.1 mol) of IM-2 are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-7.
The structural formula of the obtained cross-linking agent PM-7 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrum is obtained Display 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 8:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-8.
The structural formula of the obtained cross-linking agent PM-8 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The C-C (=O) -O C-O bond has a telescopic vibration absorption peakThe above information demonstrates successful synthesis of the crosslinker.
Synthesis example 9:
120.00g of NMP and 28.84g (0.1 mol) of IM-4 are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-9.
The structural formula of the obtained cross-linking agent PM-9 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 10:
120.00g of NMP and 34.24g (0.1 mol) of IM-5 are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 35 ℃, and a solution obtained by diluting 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal with 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-10.
The structural formula of the obtained cross-linking agent PM-10 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 11:
120.00g of NMP and 12.51g of IM-1 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-11.
The structural formula of the obtained cross-linking agent PM-11 is shown in the figure, and the cross-linking agent PM-11 is detected according to the aboveThe method is used for carrying out infrared spectrum test on the crosslinking agent, and the spectrogram shows that 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 12:
120.00g of NMP and 12.61g of IM-2 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-12.
The structural formula of the obtained cross-linking agent PM-12 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 13:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-13.
The structural formula of the obtained cross-linking agent PM-13 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 14:
120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-14.
The structural formula of the obtained cross-linking agent PM-14 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 15:
120.00g of NMP and 34.24g of IM-5 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-15.
The structural formula of the obtained cross-linking agent PM-15 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 16:
120.00g of NMP and 12.51g of IM-1 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-16.
The structural formula of the obtained cross-linking agent PM-16 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The c=o bond of C-C (=o) -O occursIs 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 17:
120.00g of NMP and 12.61g of IM-2 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-17.
The structural formula of the obtained cross-linking agent PM-17 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 18:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-18.
The structural formula of the obtained cross-linking agent PM-18 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 19:
120.00g of NMP and 28.84g of IM-4 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-19.
The structural formula of the obtained cross-linking agent PM-19 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 20:
120.00g of NMP and 34.24g of IM-5 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 35 ℃, and a solution obtained by 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped into the three-necked flask, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-20.
The structural formula of the obtained cross-linking agent PM-20 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak 173 of C-N bond of-CONH appears at0cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 21
120.00g of NMP and 42.35g of IM-6 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 53.62g (0.45 mol) of N, N-dimethylformamide dimethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-21.
The structural formula of the obtained cross-linking agent PM-21 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of the NH2 at the position disappears, namely 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 22:
120.00g of NMP and 35.44g of IM-3 (0.1 mol) are sequentially added into a 500mL three-necked flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 35 ℃, and a solution obtained by adding 66.25g (0.45 mol) of N, N-dimethylformamide diethyl acetal diluted by 50.00g of NMP is dripped, and after the dripping is completed, the reaction is 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-22.
The structural formula of the obtained cross-linking agent PM-22 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peak of the asymmetric stretching vibration and the symmetric stretching vibration of (2) disappears, and 1640cm -1 ～1660cm -1 Vibration absorption peak of C=O bond of-CONH appears at 1540cm -1 ～1550cm -1 Vibration absorption peak of C-N bond of-CONH appears at 1730cm -1 ～1740cm -1 The peak of the stretching vibration absorption of C=O bond of C-C (=O) -O appears, 1210cm -1 ～1165cm -1 The above information demonstrates successful synthesis of the crosslinker, with the appearance of a telescopic vibration absorption peak of the C-C (=o) -O C-O bond.
Synthesis example 23:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 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 solution is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is added into the reaction system, after stirring uniformly, 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-23.
The structural formula of the obtained cross-linking agent PM-23 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration disappear and are at 1780cm -1 An antisymmetric telescopic vibration absorption peak of an imide ring C=O appears at the left and right, 1380cm -1 The above information demonstrates successful synthesis of the crosslinker, with the occurrence of a nearby extension vibration absorption peak of the imide ring C-O bond.
Synthesis example 24:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 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 solution is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is added into the reaction system, after stirring uniformly, 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-24.
The structural formula of the obtained cross-linking agent PM-24 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration disappear and are at 1780cm -1 An antisymmetric telescopic vibration absorption peak of an imide ring C=O appears at the left and right, 1380cm -1 The above information demonstrates successful synthesis of the crosslinker, with the occurrence of a nearby extension vibration absorption peak of the imide ring C-O bond.
Synthesis example 25:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 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 solution is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is added into the reaction system, 61.26g (0.6 mol) of acetic anhydride is slowly added after stirring uniformly, 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-25.
The structural formula of the obtained cross-linking agent PM-25 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration disappear and are at 1780cm -1 An antisymmetric telescopic vibration absorption peak of an imide ring C=O appears at the left and right, 1380cm -1 The above information demonstrates successful synthesis of the crosslinker, with the occurrence of a nearby extension vibration absorption peak of the imide ring C-O bond.
Synthesis example 26:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 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 solution is cooled to 25 ℃, 47.46g (0.6 mol) of pyridine is added into the reaction system, 61.26g (0.6 mol) of acetic anhydride is slowly added after stirring uniformly, 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 obtained. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-26.
The structural formula of the obtained cross-linking agent PM-26 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration disappear and are at 1780cm -1 An antisymmetric telescopic vibration absorption peak of an imide ring C=O appears at the left and right, 1380cm -1 The above information demonstrates successful synthesis of the crosslinker, with the occurrence of a nearby extension vibration absorption peak of the imide ring C-O bond.
Synthesis example 27:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 61.26g (0.3 mol) of AD-1 is slowly added, after the addition is completed, the reaction is carried out for 10 hours at 80 ℃, after the reaction is completed, the reaction solution is cooled to 25 ℃, and the reaction solution is poured into 3L of deionized water, so that white precipitate is precipitated. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-27.
The structural formula of the obtained cross-linking agent PM-27 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration of (C) disappear, and the absorption peak is at 1710cm -1 The stretching vibration absorption peak of the c=o bond of-COOH appears on the left and right sides, and the above information demonstrates successful synthesis of the crosslinking agent.
Synthesis example 28:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 42.04g (0.3 mol) of AD-2 is slowly added, after the addition is completed, the reaction is carried out for 10 hours at 80 ℃, after the reaction is completed, the reaction solution is cooled to 25 ℃, and the reaction solution is poured into 3L of deionized water, so that white precipitate is precipitated. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-28.
The structural formula of the obtained cross-linking agent PM-28 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows 3400cm -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration of (C) disappear, and the absorption peak is at 1710cm -1 The stretching vibration absorption peak of the c=o bond of-COOH appears on the left and right sides, and the above information demonstrates successful synthesis of the crosslinking agent.
Synthesis example 29:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 51.64g (0.3 mol) of AD-3 is slowly added, after the addition is completed, the reaction is carried out for 10 hours at 80 ℃, after the reaction is completed, the reaction solution is cooled to 25 ℃, and the reaction solution is poured into 3L of deionized water, so that white precipitate is precipitated. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-29.
DD220105I
The structural formula of the obtained cross-linking agent PM-29 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration of (C) disappear, and the absorption peak is at 1710cm -1 The stretching vibration absorption peak of the c=o bond of-COOH appears on the left and right sides, and the above information demonstrates successful synthesis of the crosslinking agent.
Synthesis example 30:
120.00g of NMP and 35.44g (0.1 mol) of IM-3 are sequentially added into a 500mL three-neck flask equipped with a stirrer and a thermometer under the protection of nitrogen, after stirring and dissolution, 55.85g (0.3 mol) of AD-4 is slowly added, after the addition is completed, the reaction is carried out for 10 hours at 80 ℃, after the reaction is completed, the reaction solution is cooled to 25 ℃, and the reaction solution is poured into 3L of deionized water, so that white precipitate is precipitated. And washing the mixture with deionized water for three times after filtering, and putting the mixture into a vacuum oven to be dried at 80 ℃ for 72 hours to obtain the cross-linking agent PM-30.
The structural formula of the obtained cross-linking agent PM-30 is shown in the figure, the cross-linking agent is subjected to infrared spectrum test according to the detection method, and the spectrogram shows that 3400cm is obtained -1 ～3500cm -1 at-NH 2 The absorption peaks of the asymmetric stretching vibration and the symmetric stretching vibration of (C) disappear, and the absorption peak is at 1710cm -1 The stretching vibration absorption peak of the C=O bond of-COOH appears left and right, and the information proves that the cross-linking agent is successfully synthesized
In the present invention, BANI-M (Wan Shigaku Kogyo Co., ltd.) having the structure shown below was compared with the crosslinking agent of the present invention:
the solubility of the crosslinking agents synthesized in this way was measured according to the method for measuring solubility of crosslinking agents described above, and the specific results are shown in Table 1.
As can be seen from Table 1, the trifunctional N-containing heterocyclic crosslinkers having amic acid ester structures synthesized in Synthesis examples 3, 8, 13 and 18 have much greater solubility in GBL, EL and PGME than the imide-based crosslinkers synthesized in Synthesis examples 22-23, and also greater solubility in the pillared petrochemical crosslinker BANI-M. The imide-structured cross-linker is essentially insoluble in PGME, severely limiting its application.
It can also be seen from Table 1 that the trifunctional N-containing heterocyclic crosslinkers having amic acid ester structures synthesized in Synthesis examples 3, 8, 13 and 18 have much higher storage stability than the crosslinkers having amic acid structures synthesized in Synthesis examples 26-29, because amic acid is very susceptible to hydrolysis side reactions, especially in high temperature and high humidity environments, which are detrimental to product applications and storage.
The above results show that the N-heterocyclic trifunctional cross-linking agent of the amic esters synthesized according to the present invention has optimal properties. According to the different application scenes, the trifunctional cross-linking agent containing N heterocycle of the amic acid esters with different structures and the proper and optimal dosage thereof can be selected.
TABLE 1 crosslinker purity and solubility test results
Preparation of photosensitive resin composition
Example 1
31.02g (0.1 mol) of ODPA and 100.00g of NMP were successively added to a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and stirred and dissolved at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was taken, and 54.41g (0.09 mol) of HFHA and 100.00g of NMP were successively added thereto and stirred for dissolution to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. 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 mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. After filtration, the mixture was washed three times with deionized water, and then placed in a vacuum oven and dried at 80℃for 72 hours to obtain polyamic acid ester P-1.
Into a three-necked flask equipped with stirring, 10.00g of the synthesized polyamic acid ester P-1, 1.00g of a crosslinking agent PM-1, 2.00g of NT-300 (manufactured by Toyo Kogyo Co., ltd., japan), 1.00g of GBL, 20.00g of EL, and 70.00g of PGME were successively added, and stirred and dissolved, and after clarification, 0.20g of gamma-glycidoxypropyl trimethoxysilane (Nanji Dimonte, KH-560), 0.15g of a leveling agent BYK-392, and 0.15g of a defoaming agent BYK-A530 were further stirred uniformly, and then filtered through a 1 μm PP filter membrane to obtain a 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 successively added to a 500mL three-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream, and stirred and dissolved at room temperature to obtain a dianhydride solution. Another three-necked flask equipped with a stirrer was charged with 32.96g (0.09 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6 FAP) and 100.00g of NMP in this order, followed by stirring and dissolution to obtain a diamine solution. And (3) dropwise adding the diamine solution into the dianhydride solution, reacting for 1h at normal temperature after the dropwise adding is finished, and then reacting for 2h at 50 ℃. 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 mixture was reacted at 50℃for 3 hours after completion of the addition. After the reaction is completed, the reaction solution is poured into 3L of deionized water, and the polymer is separated out to obtain white precipitate. After filtration, the mixture is washed three times by deionized water, and is put into a vacuum oven to be dried for 72 hours at 80 ℃ to obtain the polyamide acid ester P-2.
Into a three-necked flask equipped with stirring, 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 Kogyo Co., ltd.), 1.00g of GBL, 20.00g of EL, and 70.00g of PGME were successively added, and stirred and dissolved, after clarification, 0.20g of KH-560,0.15g of BYK-392, and 0.15g of BYK-A530 were further added, and after continuing to stir uniformly, filtration was performed with a 1 μm PP filter membrane 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, and 15.82g of pyridine was added dropwise with stirring at 10℃or lower to obtain a reaction mixture, which was naturally heated to 25℃and stirred for 12 hours.
Next, under ice bath conditions, the reaction mixture was added to a GBL solution of 50.00g in which 41.25g (0.2 mol) of Dicyclohexylcarbodiimide (DCC) was dissolved, stirred for 40 minutes, a GBL solution of 70.00g in which 19.03g (0.095 mol) of 4,4' -diaminodiphenyl ether (ODA) was dissolved was added for 60 minutes under nitrogen, naturally warmed to 25℃and 80.00g of GBL was added, stirring was continued for 12 hours, 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, and then 300mL of tetrahydrofuran was used to dissolve the precipitated polymer, the obtained polymer solution was dropped into 5L of ultrapure water to precipitate a polymer precipitate, and the obtained precipitate was filtered off and then vacuum-dried at 50℃for 72 hours to obtain polyamic acid ester P-3.
In a three-necked flask equipped with stirring, 10.00g of synthesized polymer P-3 was dissolved in 20.00g of NMP, after complete dissolution, 1.00g of crosslinking agent PM-13, 1.00g of 3- (triethoxysilylthio) propyltrimethoxysilane (Japanese Koshi chemical, X-12-1056 ES), 0.20g of KH-560 were added, stirring was continued until complete dissolution, and then 0.30g of photoinitiator 1- (4-phenylthio-phenyl) -octyl-1, 2-dione-2-oxime-0-benzoate (OXE-1, BASF), 1.50g of crosslinking agent tetraethyleneglycol dimethacrylate (TEGDMA), and 0.10g of polymerization inhibitor P-hydroxyanisole (MEHQ) were sequentially added, and after complete dissolution, filtration was carried out with a 1.0 μm filter membrane 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 repeated 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-t-butylphenol (DMOM-PTBP-MF, benzhou chemical).
Comparative example 11
Example 1 was repeated except that a crosslinking agent was not added to the system.
The photosensitive resin compositions of examples and comparative examples were characterized in terms of film forming property, imidization rate, glass transition temperature, tensile strength, and dielectric constant by the test methods described above, and the specific results are shown in Table 2.
As can be seen from table 2: as can be seen from a comparison of examples 1 to 21 and comparative examples 9 to 11, the cured films containing the N-heterocyclic crosslinking agent of the present invention exhibited a higher imidization rate, which was significantly superior to the pilling petrochemical crosslinking agent, other types of crosslinking agents, or no crosslinking agent added. Examples 3, 8, 13, 18 and comparative examples 1 to 4 show that the crosslinking agent having the amic acid ester structure has better compatibility with the polymer and higher solubility in GBL, EL, PGME, and thus shows better effect of improving imidization rate, glass transition temperature and tensile strength than the imide structure, and the crosslinking agent having the imide structure cannot function in the composition system due to poor solubility, and thus the prepared cured film has poor performance. As can be seen from the comparison of examples 1 to 21 and comparative examples 9 to 11, the N-heterocyclic ring-containing crosslinking agent of the present invention has a great promoting effect on the film forming property of the cured film, and can have excellent film forming property at a curing temperature of 250℃at a low temperature, indicating that the N-heteroatom in the crosslinking agent has a promoting effect on imidization, as compared with other crosslinking agents or no crosslinking agent added. As is clear from comparison of examples 13 and 22 to 25, when the amount of the crosslinking agent added is too small, the effect of the cured film is not remarkable, and when the amount of the crosslinking agent added is too large, the film is brittle due to too high crosslinking degree, but the film forming property is poor, and therefore, the amount of the crosslinking agent added in the present invention is preferably 5 to 20% by mass of the resin, although the imidization rate and the glass transition temperature are very high. Examples 3, 8, 13, 18 and comparative examples 5 to 8 show that the crosslinking agent having the amic acid structure is not preferable because of its poor storage stability, although it also shows good film properties. In addition, it is apparent from examples 1 to 21 and comparative examples 9 to 11 that the compositions to which the N-containing heterocyclic cross-linking agent of the present invention is added exhibit lower dielectric constant when cured, and can be well applied to passivation insulating layers of OLED devices.
TABLE 2 photosensitive resin composition cured film Performance test results
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While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (12)

1. A trifunctional crosslinking agent, wherein the trifunctional crosslinking agent has a structure according to formula i:
wherein W is selected from the following structural formulas:
X 1 、X 2 、X 3 selected from any one of the structures shown in the general formulas II-IV
X 1 、X 2 、X 3 Is of the same structure;
in the general formulas II to IV:
R 1 one selected from methyl, ethyl and propyl;
R 2 、R 3 is a hydrogen atom;
R 4 selected from the group consisting ofOne of them.
2. A method of preparing the trifunctional crosslinking agent of claim 1, comprising the steps of:
s1, reacting a mixture containing anhydride, an N heterocyclic compound and an organic solvent to obtain precursor liquid;
s2, adding an esterification reagent into the precursor liquid, and reacting II to obtain a trifunctional cross-linking agent;
In step S1, the anhydride is selected from any one of the following structures:
wherein R is 2 、R 3 、R 4 The same claim 1;
in step S1, the N heterocyclic compound is selected from compounds represented by the following structures:
in step S2, the esterifying reagent is at least one selected from the group consisting of N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, and N, N-dimethylformamide dipropylacetal.
3. The method according to claim 2, wherein 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, dimethylsulfoxide, ethyl acetate, butyl acetate, ethyl lactate, toluene, xylene, diethylene glycol dimethyl ether.
4. The method according to claim 2, wherein in step S1, the molar ratio of the acid anhydride to the N-heterocyclic compound is 3:0.9 to 1.1.
5. The preparation method according to claim 2, wherein in step S1, the mass ratio of the acid anhydride to the organic solvent is 5 to 50:100.
6. the process according to claim 2, wherein in step S1, the conditions of reaction i are as follows:
The temperature is 10-150 ℃;
the time is 3-24 hours.
7. The preparation method according to claim 2, wherein 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.
8. the process according to claim 2, wherein in step S2, the conditions of reaction ii are as follows:
the temperature is 20-80 ℃;
the time is 2-24 hours.
9. A photosensitive resin composition characterized by comprising the following components:
component a: at least one of polyamic acid and polyamic acid ester;
component b: a trifunctional crosslinking agent;
component c: a sensitizer;
component d: a solvent;
component e: at least one of a silane coupling agent, a leveling agent and a defoaming agent;
the trifunctional crosslinking agent is selected from the trifunctional crosslinking agents described in claim 1.
10. The photosensitive resin composition according to claim 9, wherein the mass ratio of the component a to the component b is 100:0.5 to 30.
11. The photosensitive resin composition according to claim 9, wherein the mass ratio of the component a to the component b is 100:5 to 20.
12. An OLED device comprising a passivation insulating layer;
The passivation insulating layer is selected from the photosensitive resin composition according to any one of claims 9 to 11.
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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

Patent 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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