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CN111909045B - End capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof - Google Patents

End capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof Download PDF

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CN111909045B
CN111909045B CN201910384714.XA CN201910384714A CN111909045B CN 111909045 B CN111909045 B CN 111909045B CN 201910384714 A CN201910384714 A CN 201910384714A CN 111909045 B CN111909045 B CN 111909045B
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polyimide precursor
group
modified polyimide
resin composition
photosensitive resin
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CN111909045A (en
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王旭
王晓伟
刘永祥
韩红彦
李青松
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Beijing Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/90—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. amino-diphenylethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
    • 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

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  • General Physics & Mathematics (AREA)
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  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a capping agent containing a crosslinkable group, a modified polyimide precursor resin, a photosensitive resin composition and application thereof. The end capping agent containing the crosslinkable group has the function of the crosslinking agent during high-temperature curing, can be applied to polyimide precursor resin synthesis to obtain modified polyimide precursor resin with the crosslinking function, has the self-crosslinking function, does not need to be externally added with the crosslinking agent, and can realize intermolecular crosslinking of the polyimide resin in the high-temperature curing process to form a network crosslinking structure, thereby improving the overall heat resistance of the photoresist, and simultaneously having the effects of improving the peeling resistance, reducing the amount of micromolecular volatile matters, improving the glass transition temperature of the photoresist and the like. Meanwhile, as the crosslinkable group reacts with the phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material can be reduced, and the stability of the device can be improved.

Description

End capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof
Technical Field
The invention belongs to the technical field of photoetching, and relates to a blocking agent containing a crosslinkable group, modified polyimide precursor resin, a photosensitive resin composition and application thereof.
Background
Polyimide has very good high and low temperature resistance, mechanical properties, dielectric properties, biocompatibility, low thermal expansion coefficient and other properties, and is widely used in the fields of electronic appliance industry, aerospace industry, advanced composite materials, fibers, engineering plastics, photoresist and the like. The photosensitive polyimide is mainly applied to photoresist in the field of microelectronics, compared with common polyimide, the photosensitive polyimide can greatly simplify the photoetching process, and is widely applied to large-scale integrated circuits, insulating interlayers, surface passivation layers, ion implantation masks and the like because the photosensitive polyimide has the characteristics of good heat resistance, mechanical properties, electrical properties, corrosion resistance and the like. At present, in order to ensure that a film layer has good performance under a spin coating or slit coating process, the defects of bubbles and the like are avoided, the photoetching adhesive is required to be not too high, and the molecular weight of corresponding polyimide resin is relatively low, so that the resin with relatively high thermal and mechanical properties is relatively poor in molecular weight, and a small molecular cross-linking agent is required to be added subsequently to form a network cross-linking structure, so that the thermodynamic property of the polyimide is improved.
JP2014157297A discloses a photosensitive resin composition of polyimide, which has a crosslinked network structure formed in a high-temperature curing process by introducing a crosslinking functional group containing a benzyl ether structure into the photosensitive resin composition, and which has an improved 5% heat loss temperature of a resist and a good solvent stripping resistance.
CN104730861a discloses a positive photosensitive resin composition comprising: an alkali-soluble resin; a photosensitive diazoquinone compound; a cross-linking agent; a thermal acid generator; a phenol compound; and an organic solvent, wherein the crosslinking agent and the thermal acid generator are contained in a weight ratio of 1:50 to 50:1, and the positive photosensitive resin composition can be cured at a low temperature, maintains a front taper during the heat curing without pattern collapse, generates a photosensitive resin film having a small amount of outgassing from a coating layer after heating and baking, and has excellent heat resistance and chemical resistance. Further, the photosensitive resin film is free from both performance deterioration due to outgas and light emission defects such as black specks, pixel shrinkage, and the like.
However, the prior art as described above all use the way of introducing a crosslinking agent to increase the molecular weight of the resin and form a network structure to improve its physical properties, but all have the following problems: (1) The externally added small molecule cross-linking agent is difficult to react completely, and has residues; (2) The cross-linking agent itself has poor heat resistance, and the heat stability of the system is affected, so that the thermal performance of the material is improved to a limited extent, and meanwhile, small molecular volatile matters are increased. Therefore, the problem of difficult improvement of thermal stability, peeling strength and mechanical properties of the photoresist is also a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a blocking agent containing a crosslinkable group, a modified polyimide precursor resin, a photosensitive resin composition and application thereof, wherein the blocking agent containing the crosslinkable group can be used in the preparation of the modified polyimide precursor resin, so that the polyimide precursor has a crosslinking function, the crosslinking group of the blocking agent can realize the intermolecular crosslinking of the polyimide resin in the high-temperature curing process without adding the crosslinking agent, and a network crosslinking structure is formed, thereby improving the overall heat resistance of the photoresist, and simultaneously having the effects of improving the stripping resistance, reducing the amount of small molecular volatile matters, improving the glass transition temperature of the photoresist and the like.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a crosslinkable group-containing capping agent having a structure according to formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Independently selected from hydrogen atom, halogen atom, hydroxy group, - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -, C x H 2xO H orAnd R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 At least one of them is selected from the group consisting of- - -C x H 2xO H or1.ltoreq.x.ltoreq.5, 0.ltoreq.i.ltoreq.5, for example x may be 1, 2, 3, 4 or 5,i may be 0, 1, 2, 3, 4 or 5; n is an integer from 1 to 5, for example 1, 2, 3, 4 or 5;
A is any one of the following groups a-g:
wherein the dashed line represents the access position of the group.
The end-capping agent containing the crosslinkable group has the function of the crosslinking agent during high-temperature curing, and can be applied to polyimide precursor resin synthesis to obtain the modified polyimide precursor resin with the crosslinking function.
Preferably, said R 1 、R 2 And R is 3 At least one of them is selected from-CH 2 OH、-CH 2 OCH 3 or-CH 2 OCH 2 CH 3 ；
Preferably, the end-capping agent containing a crosslinkable group is any one of the following compounds:
in a second aspect, the present invention provides a modified polyimide precursor resin having a structure represented by formula II:
wherein R is a Is any one of an organic group containing aryl of C6-C30 or cycloalkyl of C3-C20;
R b is an organic group containing an aryl group of C6 to C30, an aliphatic hydrocarbon group of C2 to C12, a cyclic alkane group of C3 to C20, an aliphatic hydrocarbon group of C2 to C12 containing Si in the main chain or an aromatic hydrocarbon group of C6 to C30 linked with the organic group containing Si;
each of p and q is independently an integer of 0 to 4; p, q are not zero, said (OH) p And (OH) q Are directly connected with aryl groups, and p and q are not 0 at the same time;
R c is a hydrogen atom or a C1-C8 alkyl group; m is ≡2, for example m is 2, 3, 4, 5, 6, 9, 10, 12, 15, 18 etc.
R isWherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Independently selected from hydrogen atom, halogen atom, hydroxy group, - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -, C x H 2xO H or->And R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 At least one of them is selected from the group consisting of- - -C x H 2xO H or->X is more than or equal to 1 and less than or equal to 5, i is more than or equal to 0 and less than or equal to 5, and n is an integer of 1-5;
a is any one of the following groups a-g:
broken lines in the structural formulae of substituents in the present inventionRepresenting the access position of the substituent.
In the present invention, the modified polyimide precursor resin has an R group containing a crosslinkable group at the endI.e. containing- - - -C x H 2xO H orThe crosslinkable group of the modified polyimide precursor resin has a self-crosslinking function, a crosslinking agent is not required to be added, a dehydration ether formation reaction is carried out between benzyl alcohol and phenolic hydroxyl groups in a high-temperature imidization process, or an ether exchange reaction is carried out between benzyl ether and phenolic hydroxyl groups, a thermal crosslinking reaction is carried out between polymer backbones, an ether bond is formed, a compact and stable crosslinked network structure is obtained, the performances of thermal stability, stripping resistance, mechanical strength and the like of the photoresist resin can be greatly improved, meanwhile, the introduction of a micromolecular crosslinking agent is avoided, and the overflow amount of micromolecular volatiles of the photoresist can be effectively reduced.
Meanwhile, as the crosslinkable group reacts with the phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material can be reduced, and the stability of the device can be improved.
That is, in the present invention, the curing mechanism of the modified polyimide precursor resin is as follows:
a) Imidization reaction: the amic acid (ester) group in the main chain of the polyamic acid resin precursor is cyclized at high temperature to remove small molecular compound (water or alcohol) to generate polyimide compound, and the reaction formula is as follows:
b) Crosslinking reaction: the invention utilizes the ether exchange reaction between benzyl ether and phenolic hydroxyl or the dehydration ether formation reaction between benzyl alcohol and phenolic hydroxyl to form a cross-linked network structure of ether bond connection between polyimide main chains, thereby improving the indexes of thermal and mechanical properties, stripping resistance, hygroscopicity and the like of the photoresist resin.
In the structure shown in the formula II, R is contained a Structural units (i.e) The species of (2) may be one or more, i.e. the structure does not only represent a single carbonyl-containing structural unit, but may be R according to the differences a And R is c And contains a plurality of structural units containing carbonyl groups as shown in the formula II. Similarly, according to different R b Optionally, a plurality of amino group-containing structural units may be contained in the structure represented by formula II (i.e)。
In the present invention, the aliphatic hydrocarbon group having Si in the main chain of C2 to C12 means that the aliphatic hydrocarbon group has Si atoms in the main chain, and may be, for example Etc.; the Si-containing organic group in the C6-C30 aromatic hydrocarbon group connected with the Si-containing organic group can be an aliphatic hydrocarbon group containing Si or an aliphatic hydrocarbon group containing-Si-O-group, and the C12-C30 aromatic hydrocarbon group connected with the Si-containing organic group can beEtc.
In the present invention, the organic group containing an aryl group of C6 to C30 includes aryl groups and groups in which aryl groups are bonded to other organic groups, and the bonding position of the organic group containing an aryl group of C6 to C30 to other groups may be on the aryl group or may not be on the aryl group, and may be exemplified Etc.
Preferably, the weight average molecular weight of the modified polyimide precursor resin is 2000-50000, for example 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 7000, 8000, 9000, 10000, 12000, 15000, 18000, 20000, 23000, 25000, 28000 or 30000, preferably 5000-30000.
Preferably, said R a (OH) p Any one selected from the following groups:
wherein the dashed line represents the access position of the group.
Preferably, said R b (OH) q Any one selected from the following groups:
wherein the dashed line represents the access position of the group.
Preferably, R is selected from any one of the following groups:
Wherein the dashed line represents the access position of the group.
In the present invention, the number of carbon atoms in the group represented by C6 to C30 in the aromatic group having an aryl group, the aromatic hydrocarbon group having a C6 to C30, and the aromatic hydrocarbon group having a C6 to C30 bonded by an organic group having Si may be, for example, 6, 8, 10, 15, 18, 20, 23, 26, 28, 30 carbon atoms, or the like; similarly, the number of carbon atoms in the cycloalkyl group of C3 to C20 may be 3, 4, 5, 6, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30 carbon atoms, etc., and the C2 to C12 aliphatic hydrocarbon group, the C2 to C12 aliphatic hydrocarbon group of C2 to C12 containing Si in the main chain, represent that the number of carbon atoms in the group may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. Likewise, the definition of the other carbon number ranges also means that the carbon number of the group can take any one of the integers within the stated range.
In a third aspect, the present invention provides a photosensitive resin composition comprising the modified polyimide precursor resin of the second aspect.
Preferably, the photosensitive resin composition comprises the following components in percentage by mass:
in the photosensitive resin composition of the present invention, the mass percentage of the modified polyimide precursor resin is 5.3wt.%, 6wt.%, 8wt.%, 10wt.%, 12wt.%, 15wt.%, 18wt.%, 20wt.%, 22wt.%, 24wt.%, 26wt.%, 28wt.%, etc., preferably 6wt.% to 20wt.%.
The mass percent of the diazonaphthoquinone sulfonate is 1wt.%, 1.5wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 4.5wt.%, 5wt.%, 5.5wt.%, 6wt.%, 6.5wt.%, 7wt.%, or 7.5wt.%, etc.
The mass percent of the auxiliary agent is 0.02 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, or 0.45 wt%, etc.
The mass percent of the solvent is 61.5wt.% to 95wt.%, e.g., 62wt.%, 65wt.%, 68wt.%, 70wt.%, 72wt.%, 75wt.%, 78wt.%, 80wt.%, 71wt.%, 86wt.%, 88wt.%, 90wt.%, 94wt.%, or the like.
Preferably, the photosensitive resin composition has a solids content of 5wt.% to 38.5wt.%, e.g., 6wt.%, 8wt.%, 10wt.%, 15wt.%, 18wt.%, 20wt.%, 22wt.%, 25wt.%, 28wt.%, 30wt.%, 32wt.%, or 36wt.%, etc., preferably 8wt.% to 30wt.%.
In the present invention, the sum of the contents of the respective components in the photosensitive resin composition is 100wt.%.
In the present invention, the solid content refers to the ratio of the sum of the mass of all the substances except the solvent in the photosensitive resin composition to the composition.
In the present invention, the solid content is preferably 5wt.% to 38.5wt.%, and an excessively low solid content may affect the film continuity and uniformity at the time of film formation of the photosensitive resin composition, whereas an excessively high solid content may cause an excessively high viscosity and further cause problems such as generation of bubbles during film formation, deterioration of flatness, and the like.
Preferably, the diazonaphthoquinone sulfonate is selected from any one or a combination of at least two of the following compounds:
wherein D is 1 、D 2 And D 3 Each independently selected from-H or DNQ groups, said DNQ groups being r, s, t are each independently selected from integers from 0 to 5, for example 0, 1, 2, 3, 4 or 5;
the diazonaphthoquinone sulfonate contains at least one DNQ group.
The photolithography mechanism of the photosensitive resin composition of the present invention is as follows: the diazonaphthoquinone group in PAC can form hydrogen bonds with groups such as phenolic hydroxyl groups and carboxyl groups in a main chain of photoresist resin, so that the solubility of the resin in the photoresist in an alkali solution is inhibited, after exposure, the diazonaphthoquinone group reacts with water to generate indene acid, so that PAC compound is easily dissolved in dilute alkali water, the alkali dissolution rate of an exposure area is improved, and a positive pattern reserved in an unexposed area is obtained; in the photolithography process, the reaction process of the diazonaphthoquinone group is as follows:
in the invention, the auxiliary agent comprises any one or at least two of a leveling agent, a coupling agent and a surfactant.
Preferably, the coupling agent is a siloxane-based coupling agent.
Preferably, the surfactant is a fluorosurfactant and/or a surfactant containing polyethylene glycol structure.
In the invention, the use of the auxiliary agent is helpful for improving the planarization degree of the film, the adhesion between the photoresist compound and the substrate, reducing the residual film after development and the like.
In the present invention, the solvent includes any one or a combination of at least two of γ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, azamethylpyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide.
In a fourth aspect, the present invention provides a use of the photosensitive resin composition described in the above third aspect in an OLED display panel;
preferably, the photosensitive resin composition is used as a device protection material, an interlayer insulation material, a buffer layer material, or a pixel division layer material in OLED fabrication.
Compared with the prior art, the invention has the following beneficial effects:
the end-capping agent containing the crosslinkable group has the function of the crosslinking agent during high-temperature curing, and can be applied to polyimide precursor resin synthesis to obtain the modified polyimide precursor resin with the crosslinking function.
The modified polyimide precursor resin has a self-crosslinking function due to the crosslinkable group, does not need an external crosslinking agent, and can effectively reduce the overflow amount of micromolecular volatile matters of the photoresist by carrying out dehydration ether formation reaction between benzyl alcohol and phenolic hydroxyl or ether exchange reaction between benzyl ether and phenolic hydroxyl in the high-temperature imidization process and carrying out thermal crosslinking reaction between polymer backbones to form ether bonds, thus obtaining a compact and stable crosslinked reticular structure, greatly improving the performances of thermal stability, stripping resistance, mechanical strength and the like of the photoresist resin, avoiding the introduction of micromolecular crosslinking agents and effectively reducing the overflow amount of the micromolecular volatile matters of the photoresist.
Meanwhile, as the crosslinkable group reacts with the phenolic hydroxyl in the polyimide main chain, all or part of the hydroxyl is consumed, the hygroscopicity of the material is reduced, and the stability of the device is improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Synthesis example 1:
synthesis of hydroxyl-containing dianhydride monomer 1:
Under nitrogen atmosphere, 10.8g (0.05 mol) of 3,3 '-dihydroxy-4, 4' -benzidine and dissolved in 50mL of gamma-butyrolactone are cooled to-15 ℃, 22.1g (0.105 mol) of 1,2, 4-trimellitic anhydride chloride is then dissolved in 50mL of gamma-butyrolactone, the latter is added dropwise to the previous solution (exothermic reaction, the reaction temperature should be kept below-5 ℃ during the dropwise addition), and the reaction is continued for 5 hours after the dropwise addition. Most of the solvent was removed by rotary evaporator, and the concentrate was poured into 300mL of toluene to precipitate, to obtain the corresponding hydroxyl group-containing dianhydride monomer 1.
Structural characterization: the method comprises the following steps: fourier transform infrared Spectrum (the instruments used in the characterization of fourier transform infrared Spectrum in the present invention are all Spectrum One infrared spectrometers from Perkin Elmer, usa), characteristic peaks: 1850cm -1 The acid anhydride group characteristic peak is 3400cm -1 At the point of-OH characteristic peak, 1650cm -1 Is characterized by amide group characteristic peaks.
Synthesis example 2:
synthesizing a hydroxyl-containing dianhydride monomer 2:
the difference from preparation example 1 is that 3,3' -dihydroxy-4, 4' -benzidine was replaced with an equal amount of 5,5' - (1, 4-phenylenedi (oxo)) bis (2-aminophenol) to give hydroxyl group-containing dianhydride monomer 2.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 1850cm -1 The acid anhydride group characteristic peak is 3400cm -1 At the point of-OH characteristic peak, 1650cm -1 Is at 1240cm of amide group characteristic peak -1 Is characterized by aromatic C-O-C characteristic peak.
Synthesis example 3:
synthesis of end-capping agent 1 containing crosslinkable groups:
1.39g (10 mmol) of m-nitrophenol are taken and dissolved in 20 mM DS SO solvent, after which 1.18g (5 mmol) of p-dibromobenzene and 3.69g (22 mmol) of CsOH.H are added 2 O, carrying out reaction for 36h in an oil bath at 150 ℃, carrying out TLC tracking reaction, and purifying the product by a column chromatography method after the reaction is completed to obtain an intermediate I;
2.94g (10 mmol) of intermediate I are taken and dissolved in 20 mM DS SO solvent, after which 1.54g (10 mmol) of 3, 5-dimethylol and 3.69g (22 mmol) of CsOH.H are added 2 O, carrying out reaction for 36h in an oil bath at 150 ℃, tracking the reaction by TLC, and purifying the product by a column chromatography method after the reaction is completed to obtain an intermediate II.
0.72g (30 mmol) of sodium hydride is taken and added into 20mL of dry anisole solution, 3.67g (10 mmol) of intermediate II is taken, 30mL of dry anisole solvent is added into the solution, the solution is added dropwise into the solution, reflux reaction is carried out for 2h after the dropwise addition is finished, 1.39g (11 mmol) of dimethyl sulfate is added into the solution, and the reflux reaction is carried out overnight. Washing the solution after the reaction, drying with anhydrous sodium sulfate, removing the solvent by reduced pressure distillation, and purifying by a column chromatography method to obtain an intermediate III;
3.95g (10 mmol) of intermediate III is taken and added into 50mL of DMF solvent, then 2.13g (1 mmol) of 5% palladium carbon is added, the mixture is stirred and reacted for 24h under the hydrogen pressure of 0.4MPa, after the reaction is finished, the mixture is filtered, the filtrate is distilled under reduced pressure to remove the solvent, and the amino end-capping agent 1 is purified by a column chromatography method.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is methylene atMethyl characteristic peak, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 4:
synthesis of end-capping agent 2 containing crosslinkable groups:
the p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into m-dibromobenzene, and m-nitrophenol is changed into p-nitrophenol, and other reaction conditions are kept unchanged, so that the end-capping agent 2 containing the crosslinkable group is obtained as follows:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 5:
synthesis of end-capping agent 3 containing crosslinkable groups:
the p-dibromobenzene used in the synthesis step of the end capping agent 1 containing the crosslinkable group is changed into the tribromobenzene, and other reaction conditions are kept unchanged to obtain an amino end capping agent 3:
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 6:
synthesis of end-capping agent 4 containing crosslinkable groups:
the p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into 1,2,4, 5-tetrabromobenzene, and other reaction conditions are kept unchanged, so that the following end-capping agent 4 containing the crosslinkable group is obtained:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 7:
synthesis of end-capping agent 5 containing crosslinkable groups:
the p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into 3,3', 5' -tetrabromobiphenyl, and other reaction conditions are kept unchanged, so that the end-capping agent 5 containing the crosslinkable group is obtained:
structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 8:
synthesis of end-capping agent 6 containing crosslinkable groups:
the p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group is changed into 2,3,6, 7-tetrabromonaphthalene, and other reaction conditions are kept unchanged, so that the end-capping agent 6 containing the crosslinkable group is obtained.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 9:
synthesis of end-capping agent 7 containing crosslinkable groups:
the synthesis method comprises the following steps: 1.39g (10 mmol) of m-nitrophenol are taken and dissolved in 20 mM DS SO solvent, after which 1.18g (5 mmol) of m-dibromobenzene and 3.69g (22 mmol) of CsOH.H are added 2 O, carrying out reaction for 36h in an oil bath at 150 ℃, carrying out TLC tracking reaction, and purifying the product by a column chromatography method after the reaction is completed to obtain an intermediate I;
2.94g (10 mmol) of intermediate I are taken and dissolved in 20 mM DS SO solvent, after which 1.54g (10 mmol) of 3, 5-dimethylol and 3.69g (22 mmol) of CsOH.H are added 2 O, carrying out reaction for 36h in an oil bath at 150 ℃, tracking the reaction by TLC, and purifying the product by a column chromatography method after the reaction is completed to obtain an intermediate II.
3.67g (10 mmol) of intermediate II is taken and added into 50mL of DMF solvent, then 2.13g (1 mmol) of 5% palladium on carbon is added, the mixture is stirred and reacted for 24h under the hydrogen pressure of 0.4MPa, after the reaction is finished, the mixture is filtered, the filtrate is distilled under reduced pressure to remove the solvent, and the amino end-capping agent 7 is purified by a column chromatography method.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak, 3250cm -1 Is at the position of-NH 2 Characteristic peak, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak.
Synthesis example 10:
synthesis of end-capping agent 8 containing crosslinkable groups:
the synthesis method comprises the following steps: the p-dibromobenzene used in the synthesis step of the end-capping reagent 1 containing the crosslinkable group is changed into 3,3', 4', 5' -hexabromobiphenyl, 3, 5-dihydroxymethylphenol is changed into 4-bromobenzyl alcohol, dimethyl sulfate is changed into diethyl sulfate, and other reaction conditions are kept unchanged, so that the end-capping reagent 8 containing the crosslinkable group is obtained
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3250cm -1 Is at the position of-NH 2 Characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl, 1240cm -1 Is characterized by aromatic C-O-C characteristic peak, 1155cm -1 The characteristic peaks of fat C-O-C are shown.
Synthesis example 11:
synthesis of polyimide precursor 1:
5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. 28.2g (50 mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP are weighed and mixed, the mixture is rapidly added into a reaction system, stirring is carried out for 3 hours, the temperature is raised to 40 ℃, 7.31g (20 mmol) of end-capping agent 1 is added, stirring is carried out for 4 hours, the temperature is raised to 50 ℃, 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal is slowly added dropwise into the reaction system, the reaction is carried out for 2 hours at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, the obtained solid precipitate is dried in vacuum for 24 hours at 80 ℃ to obtain polyimide precursor 1, and the molecular weight is 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 12
Synthesis of modified polyimide precursor 2
The blocking agent 1 in synthesis example 12 was replaced with an equal amount of blocking agent 2 to give the corresponding polyimide precursor 2 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 13
Synthesis of modified polyimide precursor 3
The blocking agent 1 in synthesis example 12 was replaced with an equal amount of blocking agent 3 to obtain a corresponding polyimide precursor 3 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 14
Synthesis of modified polyimide precursor 4
The blocking agent 1 in synthesis example 12 was replaced with an equal amount of blocking agent 4 to obtain a corresponding polyimide precursor 4 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 15
Synthesis of modified polyimide precursor 5
The blocking agent 1 in synthesis example 12 was replaced with an equal amount of blocking agent 5 to obtain a corresponding polyimide precursor 5 having a molecular weight of 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 16
Synthesizing a modified polyimide precursor 6:
4.24g (15 mmol) of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone, 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4 ℃. 28.2g (50 mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP are weighed and mixed, the mixture is rapidly added into a reaction system, stirring is carried out for 3 hours, the temperature is raised to 40 ℃, 14.50g (20 mmol) of end-capping agent 4 is added, stirring is carried out for 4 hours, the temperature is raised to 50 ℃, 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal is slowly added dropwise into the reaction system, the reaction is carried out for 2 hours at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, the obtained solid precipitate is dried in vacuum for 24 hours at 80 ℃ to obtain polyimide precursor 6, and the molecular weight is 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 is-CO characteristic peak in-CONH, 1150cm -1 At the position of-SO 2 Characteristic peaks.
Synthesis example 17
Synthesizing a modified polyimide precursor 7:
8.02g (40 mmol) of 4,4' -diaminodiphenyl ether are introduced into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) are added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. 28.2g (50 mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP are weighed and mixed, the mixture is rapidly added into a reaction system, stirring is carried out for 3 hours, the temperature is raised to 40 ℃, 14.50g (20 mmol) of amino end-capping agent 4 is added, stirring is carried out for 4 hours, the temperature is raised to 50 ℃, 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal is slowly dripped into the reaction system, after reacting for 2 hours at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, the obtained solid precipitate is dried for 24 hours at 80 ℃ in vacuum, and polyimide precursor 7 with molecular weight of 7000 is obtained.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is a characteristic peak of-CO in-CONH.
Synthesis example 18
Synthesizing a modified polyimide precursor 8:
4.24g (15 mmol) of 3,3' -diamino-4, 4' -dihydroxydiphenyl sulfone, 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4 ℃. And (2) weighing 15.51g (50 mmol) of 4,4' -diphenyl ether tetracarboxylic dianhydride, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3h, heating to 40 ℃, adding 14.50g (20 mmol) of amino end-capping agent 4, stirring for reaction for 4h, heating to 50 ℃, slowly dripping 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting at 50 ℃ for 2h, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate at 80 ℃ for 24h to obtain polyimide precursor 8 with molecular weight 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak 3400-3500 cm -1 Characteristic peak is-COOH specialPeak syndrome, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 is-CO characteristic peak in-CONH, 1150cm -1 At the position of-SO 2 Characteristic peaks.
Synthesis example 19
Synthesis of modified polyimide precursor 9
The synthesis method comprises the following steps: 5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. And (2) weighing 35.0g (52 mmol) of hydroxyl-containing dianhydride monomer 2, mixing with 35mL of NMP, quickly adding into a reaction system, stirring for reaction for 3 hours, heating to 40 ℃, adding 17.4g (24 mmol) of end-capping agent 4, stirring for reaction for 4 hours, heating to 50 ℃, slowly dripping 9.91g (83.2 mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting at 50 ℃ for 2 hours, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate at 80 ℃ for 24 hours to obtain polyimide precursor 9 with molecular weight of 5000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 20
Synthesis of modified polyimide precursor 10
The synthesis method comprises the following steps: 5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. 28.2g (42 mmol) of hydroxyl-containing dianhydride monomer 2 and 35mL of NMP are weighed and mixed, added into a reaction system for stirring reaction for 3 hours, then heated to 40 ℃, 3.1g (4 mmol) of end-capping agent 6 is added, stirring reaction is carried out for 4 hours, heated to 50 ℃, 8.0g (67.2 mmol) of N, N-dimethylformamide dimethyl acetal is slowly dripped into the reaction system for reaction for 2 hours at 50 ℃, then the obtained solution is added into 1L of deionized water for precipitation, and the obtained solid precipitate is dried for 24 hours at 80 ℃ in vacuum, thus obtaining polyimide precursor 10 with molecular weight of 30000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 21
Synthesis of modified polyimide precursor 11
The synthesis method comprises the following steps: 5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. And (2) mixing 53.8g (80 mmol) of hydroxyl-containing dianhydride monomer 2 with 35mL of NMP, rapidly adding the mixture into a reaction system, stirring and reacting for 3 hours, heating to 40 ℃, adding 27.0g (80 mmol) of end-capping agent 7, stirring and reacting for 4 hours, heating to 50 ℃, slowly dripping 15.2g (128 mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate at 80 ℃ for 24 hours to obtain polyimide precursor 11 with the molecular weight of 2000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 22
Synthesis of polyimide precursor 12
Synthesis method 5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4 ℃. And (2) 27.1g (40.4 mmol) of hydroxyl-containing dianhydride monomer 2 and 35mL of NMP are weighed and mixed, added into a reaction system twice, stirred and reacted for 3 hours, heated to 40 ℃, 0.81g (0.8 mmol) of end-capping agent 8 is added, stirred and reacted for 4 hours, heated to 50 ℃, 8.0g (67.2 mmol) of N, N-dimethylformamide dimethyl acetal is slowly added into the reaction system in a dropwise manner, reacted for 2 hours at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, and the obtained solid precipitate is dried for 24 hours at 80 ℃ in vacuum to obtain polyimide precursor 12 with molecular weight of 50000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Synthesis example 23
Synthesizing a modified polyimide precursor 13:
4.24g (15 mmol) of 3,3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 2.85g (25 mmol) of 1, 4-cyclohexanediamine (TCI, CAS: 3114-70-3) were weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. 11.21g (50 mmol) of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (TCI, CAS: 2754-41-8) was additionally weighed and mixed with 35mL of NMP, and rapidly added into the reaction system, after stirring and reacting for 3 hours, the temperature was raised to 40 ℃, 14.50g (20 mmol) of amino-terminated agent 4 was added, stirring and reacting for 4 hours, the temperature was raised to 50 ℃, 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal was slowly added dropwise into the reaction system, after reacting for 2 hours at 50 ℃, the obtained solution was added into 1L of deionized water to precipitate, and the obtained solid precipitate was vacuum-dried at 80 ℃ for 24 hours to obtain polyimide precursor 13, the molecular weight of which was 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 is-CO characteristic peak in-CONH, 1150cm -1 At the position of-SO 2 Characteristic peaks.
Synthesis example 24
Synthesis of modified polyimide precursor 14:
1.74g (15 mmol) of 1, 6-hexamethylenediamine (carbofuran, CAS: 124-09-4), 6.21g (25 mmol) of 1, 3-bis (3-aminopropyl) -1,1', 3' -tetramethyldisiloxane (TCI, CAS: 2469-55-8) are weighed into a 250mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) are added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. And (2) weighing 33.6g (50 mmol) of hydroxyl-containing dianhydride monomer, mixing with 35mL of NMP, rapidly adding into a reaction system, stirring for reaction for 3 hours, heating to 40 ℃, adding 14.50g (20 mmol) of amino end-capping agent 4, stirring for reaction for 4 hours, heating to 50 ℃, slowly dripping 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting at 50 ℃ for 2 hours, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate at 80 ℃ for 24 hours to obtain polyimide precursor 14 with molecular weight 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3200-3400 cm -1 The broad peak is-OH characteristic peak 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is the characteristic peak of-CO in-CONH, 1020cm -1 At the point of-Si-O characteristic peak, 800cm -1 The peak is-Si-C characteristic.
Synthesis example 25
Synthesis of modified polyimide precursor 15
The synthesis method comprises the following steps: 5.49g (15 mmol) of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 6.86g (25 mmol) of bis (4-aminophenoxy) dimethylsilane (carbofuran, CAS: 1223-16-1) were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. And (2) mixing 33.6g (50 mmol) of hydroxyl-containing dianhydride monomer 2 with 35mL of NMP, rapidly adding into a reaction system, stirring for reaction for 3 hours, heating to 40 ℃, adding 14.5g (20 mmol) of end-capping agent 4, stirring for reaction for 4 hours, heating to 50 ℃, slowly dripping 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal into the reaction system, reacting for 2 hours at 50 ℃, adding the obtained solution into 1L of deionized water for precipitation, and vacuum drying the obtained solid precipitate at 80 ℃ for 24 hours to obtain polyimide precursor 15 with molecular weight 7000.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristic peaks: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peak, 1020cm -1 At the point of-Si-O characteristic peak, 800cm -1 The peak is-Si-C characteristic.
Comparative synthesis example 1:
synthesis of unmodified polyimide precursor 1:
5.49g (15 mmol) of 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5.01g (25 mmol) of 4,4' -diaminodiphenyl ether were weighed into a 250mL three-necked flask, and 50mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere and dissolved by mechanical stirring at 4 ℃. 28.2g (50 mmol) of hydroxyl-containing dianhydride monomer 1 and 35mL of NMP are weighed and mixed, the mixture is rapidly added into a reaction system, stirring is carried out for 3 hours, the temperature is raised to 40 ℃, 1.86g (20 mmol) of aniline is added, stirring is carried out for 4 hours, the temperature is raised to 50 ℃, 9.53g (80 mmol) of N, N-dimethylformamide dimethyl acetal is slowly added dropwise into the reaction system for 2 hours at 50 ℃, the obtained solution is added into 1L of deionized water for precipitation, the obtained solid precipitate is dried in vacuum for 24 hours at 80 ℃, and the molecular weight is 7000, thus obtaining the unmodified polyimide precursor 1.
Structural characterization: the method comprises the following steps: fourier transform infrared spectrum, characteristicsPeak: 3400-3500 cm -1 The characteristic peak is-COOH characteristic peak, 3200-3400 cm -1 The broad peak is-OH characteristic peak, 2850cm -1 ～2950cm -1 Is characterized by methylene and methyl characteristic peaks at 1720cm -1 Is characterized by a characteristic peak of-CO in carboxyl, 1650cm -1 Is located at the characteristic peak of-CO in-CONH, 1350cm -1 at-CF 3 Characteristic peaks.
Example 1
The present embodiment provides a photosensitive resin composition prepared by the following method:
5g of modified polyimide precursor resin 1 is weighed and dissolved in 50mL of mixed solvent composed of 40% gamma-butyrolactone, 20% ethyl lactate and 40% propylene glycol monomethyl ether, 1g of PAC-1,0.01g of silane coupling agent and 0.02g of fluorine-containing surfactant are added, and after stirring and dissolution, the mixture is filtered through a 0.45-micrometer filter to obtain a photosensitive polyimide resin composition 1.
Example 2
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 2 of equal mass, and the photosensitive polyimide resin composition 2 was produced in the same manner.
Example 3
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 3 of equal mass, and the photosensitive polyimide resin composition 3 was produced in the same manner.
Example 4
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 4 of equal mass, and a photosensitive polyimide resin composition 4 was produced in the same manner.
Example 5
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 5 of equal mass, and the photosensitive polyimide resin composition 5 was produced in the same manner.
Example 6
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 6 of equal mass, and a photosensitive polyimide resin composition 6 was produced in the same manner.
Example 7
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 7 of equal mass, and the photosensitive polyimide resin composition 7 was produced in the same manner.
Example 8
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 8 of equal mass, and the photosensitive polyimide resin composition 8 was produced in the same manner.
Example 9
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 9 of equal mass, and the photosensitive polyimide resin composition 9 was produced in the same manner.
Example 10
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 10 of equal mass, and the photosensitive polyimide resin composition 10 was produced in the same manner.
Example 11
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 11 of equal mass, and the photosensitive polyimide resin composition 11 was produced in the same manner.
Example 12
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 12 of equal mass, and the photosensitive polyimide resin composition 12 was produced in the same manner.
Example 13
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with a modified polyimide precursor 13 of equal mass, and the photosensitive polyimide resin composition 13 was produced in the same manner.
Example 14
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with the modified polyimide precursor 12 of equal mass, and a photosensitive polyimide resin composition 14 was produced in the same manner.
Example 15
This example provides a photosensitive resin composition differing from example 1 in that the modified polyimide precursor 1 was replaced with the modified polyimide precursor 12 of equal mass, and a photosensitive polyimide resin composition 15 was produced in the same manner.
Comparative example 1
The difference from example 1 is that the modified polyimide precursor 1 was replaced with an unmodified polyimide precursor 1 of equal mass to obtain a photosensitive resin composition D1.
Comparative example 2
The difference from example 1 is that the modified polyimide precursor 1 was replaced with an unmodified polyimide precursor 1 of equal mass, and 1.0g of a blocking agent 4 containing a crosslinkable group was added as a crosslinking agent to obtain a photosensitive resin composition D2.
Photolithography performance test:
the prepared photosensitive polyimide resin composition was spin-coated on a 5-inch square glass substrate, pre-baked at 120 ℃ for 180 seconds to remove most of the solvent, then exposed to an ultraviolet exposure machine at 365nm, developed with 2.38% tetramethylammonium hydroxide (2.38 wt.% TMAH) for 60s to 120s to obtain a photolithographic pattern, and the minimum exposure required for developing the complete pattern at a sensitivity of 60 s.
Outgas (Small molecule volatilization) test:
sample preparation: the prepared photosensitive resin composition was applied to a 5-inch square glass substrate by spin coating (note: wherein the samples of examples 10, 12 and comparative example 2 were high in viscosity due to their large molecular weight, so the gumming speed was adjusted to 1000rpm, the sample of example 11 was low in molecular weight, low in viscosity, the rotational speed was adjusted to 200rpm, and the coating was performed at a rotational speed of 250rpm in the remaining examples and comparative examples), pre-baked at 120℃for 180 seconds to remove most of the solvent, and then the coated glass substrate was cured for 1 hour under nitrogen protection (oxygen concentration <500 ppm) in a clean oven at 250℃and the film was scraped off and vacuum-sealed and stored for use.
Thermogravimetric analysis test: test atmosphere: nitrogen gas, temperature program: and (3) preserving the temperature at 40 ℃ for 30min, then raising the temperature to 250 ℃ at a rate of 5K/min, preserving the temperature for 30min, and calculating the mass loss in the heat preservation process at 250 ℃.
Peel resistance test:
the prepared photosensitive polyimide resin composition was spin-coated (rotation speed, 250 rpm) on a 5-inch square glass substrate, pre-baked at 120℃for 180 seconds to remove most of the solvent, measured for film thickness t, and then placed in a nitrogen clean oven (oxygen concentration) at 250 ℃ <500 ppm) was cured for 1 hour, and the film thickness t was measured by ellipsometry 1 . Soaking the coated glass substrate in 65 ℃ TOK106 stripping solution, etching for 150s, taking out, washing with deionized water, and cleaning the oven with nitrogen at 230 ℃ to obtain the final product<500 ppm) was baked for 30min and the film thickness t was measured with an ellipsometer 2 The film thickness variation Δt=t before and after etching was calculated 2 -t 1 。
The results of the above performance tests are shown in Table 1.
TABLE 1
Mechanical property test:
pouring the photosensitive resin composition into a 150mm (10 mm) and 0.5mm (long (wide) deep) mold, placing the mold on a horizontal table, airing the mold to be semi-dry at room temperature, placing the mold in a nitrogen oven, and solidifying the mold according to a temperature program of 100 ℃ (30 min) -130 ℃ (30 min) -150 ℃ (30 min) -200 ℃ (30 min) -250 ℃ (60 min) -naturally cooling to room temperature to obtain a test standard spline, wherein the film thickness is 20 mu m, and testing mechanical properties by a universal material tester at a displacement rate of 5mm/min and an environment of 23 ℃ and humidity of 50+/-5%.
The mechanical properties are shown in Table 2.
TABLE 2
Tensile Strength (MPa) Elongation at break (%)
Example 1 100 10
Example 2 100 10
Example 3 110 12
Example 4 150 15
Example 5 150 15
Example 6 150 15
Example 7 95 9
Example 8 95 9
Example 9 92 8
Example 10 150 20
Example 11 90 6
Example 12 180 25
Example 13 85 6
Example 14 65 5
Example 15 100 10
Comparative example 1 20 2
Comparative example 2 80 5
From the data analysis in tables 1 and 2, compared with comparative example 1 without crosslinking, the polyimide precursor photosensitive resin composition with crosslinking function prepared by the invention has good comprehensive properties such as photoetching performance, heat resistance, mechanical property, low-molecular-weight volatile (outgas) and the like, and has excellent application potential. The examples in the table show that the density and content of the crosslinking groups have a greater influence on the overall performance of the photoresist, and the higher the density of the crosslinking sites (hydroxyl groups) in the resin, the more favorable the polyimide resin to form a body-type crosslinking structure in the curing process, the improved peeling resistance of the resin and the reduced outgas of the resin.
If a blocking agent containing a crosslinkable group is added as a small molecule component to the photosensitive resin composition (i.e., comparative example 2), the peeling resistance can be significantly improved and the outgas can be reduced as well, but the effect is inferior to that of a resin synthesized directly using an amino blocking agent of a corresponding structure. However, the heat resistance, mechanical properties, low molecular weight volatile (outgas) and other comprehensive properties of the resin can be greatly improved in comparative example 2 compared with comparative example 1 without crosslinking.
The applicant states that the present invention is illustrated by the above examples for the capping agent containing a crosslinkable group, the modified polyimide precursor resin, the photosensitive resin composition and the use thereof, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced depending on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (14)

1. A crosslinkable group-containing capping agent, characterized in that the crosslinkable group-containing capping agent has a structure according to formula I:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Independently selected from hydrogen atoms, -C x H 2x OH orAnd R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 At least one of them is selected from the group consisting of- - -C x H 2x OH or->X is more than or equal to 1 and less than or equal to 5, i is more than or equal to 0 and less than or equal to 5; n is an integer of 1 to 5;
a is any one of the following groups a-g:
wherein the dashed line represents the access position of the group.
2. According to claimThe blocking agent containing a crosslinkable group as claimed in claim 1, wherein R 1 、R 2 And R is 3 At least one of them is selected from-CH 2 OH、-CH 2 OCH 3 or-CH 2 OCH 2 CH 3 。
3. The crosslinkable group-containing capping agent of claim 1 wherein the crosslinkable group-containing capping agent is any one of the following compounds:
4. A modified polyimide precursor resin, characterized in that the modified polyimide precursor resin has a structure represented by the following formula II:
wherein R is a Is any one of an organic group containing aryl of C6-C30 or cycloalkyl of C3-C20;
R b is an organic group containing an aryl group of C6 to C30, an aliphatic hydrocarbon group of C2 to C12, a cycloalkyl group of C3 to C20, an aliphatic hydrocarbon group of C2 to C12 containing Si in the main chain or an aromatic hydrocarbon group of C6 to C30 linked with an organic group containing Si;
each of p and q is independently an integer of 0 to 4; p, q are not zero, said (OH) p And (OH) q Are directly connected with aryl groups, and p and q are not 0 at the same time;
R c is a hydrogen atom or a C1-C8 alkyl group; m is more than or equal to 2;
r isWherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 Independently selected from hydrogen atoms, -C x H 2xO H or->And R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 At least one of them is selected from the group consisting of- - -C x H 2xO H or1≤ x Not less than 5, not less than 0 and not more than 5, n is an integer of 1 to 5;
a is any one of the following groups a-g:
wherein the dashed line represents the access position of the group.
5. The modified polyimide precursor resin according to claim 4, wherein the modified polyimide precursor resin has a weight average molecular weight of 2000 to 50000.
6. The modified polyimide precursor resin according to claim 4, wherein the modified polyimide precursor resin has a weight average molecular weight of 5000 to 30000.
7. The modified polyimide precursor resin according to claim 4, wherein said R a (OH) p Any one selected from the following groups:
wherein the dashed line represents the access position of the group.
8. The modified polyimide precursor resin according to claim 4, wherein said R b (OH) q Any one selected from the following groups:
wherein the dashed line represents the access position of the group.
9. The modified polyimide precursor resin according to claim 4, wherein R is selected from any one of the following groups:
wherein the dashed line represents the access position of the group.
10. A photosensitive resin composition comprising the modified polyimide precursor resin of any one of claims 4 to 9.
11. The photosensitive resin composition of claim 10, wherein the photosensitive resin composition has a solids content of 5wt.% to 38.5wt.%.
12. The photosensitive resin composition of claim 10, wherein the photosensitive resin composition has a solids content of 8wt.% to 30wt.%.
13. Use of the photosensitive resin composition according to any one of claims 10 to 12 in an OLED display panel.
14. The use according to claim 13, wherein the photosensitive resin composition is used as a device protection material, an interlayer insulation material, a buffer layer material or a pixel division layer material in OLED fabrication.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07145282A (en) * 1993-10-01 1995-06-06 Asahi Chem Ind Co Ltd Modified polyphenylene ether resin composition
JP2007133377A (en) * 2005-10-12 2007-05-31 Toray Ind Inc Photosensitive resin composition
JP2009009107A (en) * 2007-05-25 2009-01-15 Toray Ind Inc Photosensitive resin composition
JP2014157297A (en) * 2013-02-18 2014-08-28 Toray Ind Inc Positive photosensitive resin composition
CN104584297A (en) * 2012-08-23 2015-04-29 株式会社可乐丽 Polyelectrolyte film
CN105367976A (en) * 2015-11-18 2016-03-02 安徽雄亚塑胶科技有限公司 Highly-wear-resistant TPE foaming shoe material and preparation method thereof
CN108059722A (en) * 2017-12-22 2018-05-22 杭州师范大学 A kind of polyarylether-polysiloxane copolymer and preparation method thereof
WO2018173840A1 (en) * 2017-03-21 2018-09-27 東レ株式会社 Photosensitive resin composition, photosensitive resin composition film, insulating film and electronic component

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI398724B (en) * 2005-03-15 2013-06-11 Toray Industries Photo-sensitive resin composition
KR102280582B1 (en) * 2016-05-25 2021-07-23 도레이 카부시키가이샤 resin composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07145282A (en) * 1993-10-01 1995-06-06 Asahi Chem Ind Co Ltd Modified polyphenylene ether resin composition
JP2007133377A (en) * 2005-10-12 2007-05-31 Toray Ind Inc Photosensitive resin composition
JP2009009107A (en) * 2007-05-25 2009-01-15 Toray Ind Inc Photosensitive resin composition
CN104584297A (en) * 2012-08-23 2015-04-29 株式会社可乐丽 Polyelectrolyte film
JP2014157297A (en) * 2013-02-18 2014-08-28 Toray Ind Inc Positive photosensitive resin composition
CN105367976A (en) * 2015-11-18 2016-03-02 安徽雄亚塑胶科技有限公司 Highly-wear-resistant TPE foaming shoe material and preparation method thereof
WO2018173840A1 (en) * 2017-03-21 2018-09-27 東レ株式会社 Photosensitive resin composition, photosensitive resin composition film, insulating film and electronic component
CN108059722A (en) * 2017-12-22 2018-05-22 杭州师范大学 A kind of polyarylether-polysiloxane copolymer and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
光敏聚酰亚胺的发展现状;孙自淑,马家举,江棂;化工新型材料(10) *
光敏聚酰亚胺的研究与应用进展;魏文康;虞鑫海;王凯;吕伦春;;合成技术及应用(03) *

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