CN114853714B

CN114853714B - Photo-crosslinkable photosensitive material and application thereof

Info

Publication number: CN114853714B
Application number: CN202210520614.7A
Authority: CN
Inventors: 肖义; 张文豪; 张新富; 陈令成
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2022-05-13
Filing date: 2022-05-13
Publication date: 2024-04-16
Anticipated expiration: 2042-05-13
Also published as: CN114853714A

Abstract

A novel photo-crosslinkable material and application thereof belong to the field of functional organic polymer materials. The photo-crosslinkable diamine material takes spiro [ fluorene-9, 9' -xanthene ] as a core, takes amino groups and phenolic hydroxyl groups on a xanthene ring as derivative sites to connect with crosslinkable photosensitive groups, and obtains different photosensitive polyimides through polymerization of fluorene ring 2, 7-diamino groups and different dibasic acid anhydrides, thus being applicable to photo-crosslinking and photo-curing materials, and being expected to be applied to the fields of photoresist, three-dimensional printing and the like.

Description

Photo-crosslinkable photosensitive material and application thereof

Technical Field

The invention belongs to the field of functional organic polymer materials, and particularly relates to a novel photo-crosslinkable photosensitive material and application thereof.

Background

Polyimide (PI) is used as a special functional polymer material, and is an aromatic heterocyclic polymer compound containing imide groups in the main chain of the molecule. The polymer molecular chain contains aromatic rings and imine rings, and the imide rings are in planar symmetrical annular structures, so that the polyimide molecules have classical Van der Waals force, dominant interlayer stacking of charge transfer complexes, mixed layer stacking and the like, and the structures jointly determine the excellent performances of high rigidity, high melting point, good heat resistance, chemical corrosion resistance, high mechanical strength, radiation resistance, good electrical insulation property, low dielectric constant, flame retardance and the like of the polyimide. Therefore, the polymer is widely applied to the fields of semiconductors, three-dimensional printing, optical waveguide materials, liquid crystal materials, nonlinear optical materials and the like, and becomes a functional polymer material with wide application prospect

Polyimide molecular main chains generally contain benzene rings and imide ring structures, and polyimide has stronger intermolecular action due to electron polarization and crystallinity, so that polyimide molecular chains are closely stacked, and the traditional polyimide is not melted or dissolved and is difficult to process. When the method is applied to the fields of semiconductors and three-dimensional printing materials, the process flow is complicated due to lack of photosensitivity, the manufacturing cost is increased, and certain limitations exist. Therefore, the method has very important significance for researching the photosensitive polyimide (PSPI) material which can not only keep the excellent performances of heat resistance, good electrical insulation and the like of the traditional polyimide, but also improve the solubility and increase the photosensitivity.

The spiro aromatic compound has the advantages of large conjugated system, unique spiro conjugated effect, rigid coplanar structure, high glass transition temperature, good heat stability and the like, and becomes an important structural unit of an organic polymer material. In the spiro aromatic hydrocarbon material, spiro [ fluorene-9, 9' -xanthene ] connects two parts of fluorene ring and xanthene ring through central sp3 hybridized C atom, and different organic groups can be used for modification at different sites, so that the spiro combined structure of the xanthene ring and the fluorene ring rich in electrons can effectively construct a non-planar three-dimensional molecular conformation in the molecular field. The steric hindrance effect can effectively inhibit pi-pi interaction between molecules, so that the solubility and stability of the material are improved. Therefore, it is very promising to research the application of the material to polyimide to improve the solubility and the like.

Disclosure of Invention

The invention researches photosensitive diamine monomer and application thereof, develops a photo-crosslinkable photosensitive diamine monomer, and the photo-crosslinkable photosensitive diamine monomer can be polymerized with different types of dibasic acid anhydride to obtain different photo-crosslinkable photosensitive polyimide, and is used as photo-crosslinking and photo-curing material, and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.

The invention firstly provides a novel photo-crosslinkable photosensitive material, which has a structure shown in a general formula Z, PAA, PSPI:

Wherein X is each independently selected from n is a number greater than 1;

specifically, n is a number from 1 to 1000;

Specifically, n is a number from 2 to 500.

R ₁,R₂ is independently selected from m which is an integer of 0-10, and R ₃ is C3-C8 cycloolefin containing substituent or not containing substituent.

The substituent is selected from C1-C20 alkane and halogen.

Specifically, R ₃ may be selected from

Y is each independently selected from the group consisting of commercial aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride.

Specifically, Y is each independently selected from the group consisting of commercial C4-C30 aliphatic tetracarboxylic dianhydride, C4-C30 cycloaliphatic tetracarboxylic dianhydride, C4-C30 aromatic tetracarboxylic dianhydride, C4-C30 heterocyclic tetracarboxylic dianhydride, and parent structures.

The parent structure is a structure other than anhydride bond on tetracarboxylic dianhydride.

Specifically, Y is each independently selected from

Specifically, the novel photo-crosslinkable photosensitive material can be selected from the following structures:

Wherein, the definition of X and Y is the same as the definition in the structural general formula.

The photocrosslinkable photosensitive diamine monomer shown in the general formula W takes spiro [ fluorene-9, 9' -xanthene ] as a core, and two perpendicular unconjugated units of the fluorene ring and the xanthene ring enable the photocrosslinkable photosensitive diamine monomer to have a three-dimensional large-volume steric hindrance rigid structure, and a series of derivatives synthesized by the photocrosslinkable photosensitive diamine monomer have higher melting point and glass transition temperature, can inhibit crystallization of molecules, have good film forming property, and improve thermodynamic stability of the molecules. The amino and phenolic hydroxyl groups on the xanthene ring are connected with photo-crosslinkable groups, so that the monomer has photosensitivity, and the 2, 7-positions of the fluorene ring have good reactivity, thereby providing convenience for the extension of the structure of the xanthene ring to a three-dimensional space. The crosslinkable photosensitive diamine monomer is polymerized with different binary acid anhydrides to obtain a series of photosensitive polyimide (shown as general formulas PAA and PSPI), can be used as photocrosslinking and photocuring materials, and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.

The preparation method of the photo-crosslinkable photosensitive material comprises the steps of constructing spiro [ fluorene-9, 9' -xanthene ] by taking fluorenone and different substituted phenols as raw materials, connecting the amino group and the phenolic hydroxyl group on the xanthene ring as derivative sites, and polymerizing the 2, 7-diamino group of the fluorene ring with different binary acid anhydrides to obtain different photosensitive polyimides, wherein the preparation method comprises the following steps:

Compound B obtained by one-step nitration of compound a:

Compound B forms a ring with a different substituted phenol (compound U) in the acid catalyzed next step to build compound C:

The compound C and the compound V are subjected to esterification reaction of acyl chloride and hydroxyl or amidation reaction of acyl chloride and amino to obtain a compound D:

wherein X is defined as in the structural general formula, and the compound V is selected from the following structures:

Wherein m=an integer of 0 to 10, and R ₃ is a cyclic olefin having 3 to 8 carbons and a derivative thereof;

the compound D and Zn powder react under acidic condition to reduce nitro to obtain a compound W:

wherein, the definition of X is the same as the definition in the structural general formula.

The compound W is polymerized with different dibasic acid anhydrides (compound K) to obtain different polyamide acid PAA or photosensitive polyimide PSPI:

Wherein X, Y is defined as the above structural formula. Selected from the group consisting of commercial aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride, wherein Y is the parent structure of the aliphatic tetracarboxylic dianhydride, cycloaliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, heterocyclic tetracarboxylic dianhydride, and the ring in/() is not used to limit that Y must be a cyclic structure.

Specifically, the preparation method of the photo-crosslinkable photosensitive material can adopt the following steps:

1) Adding the compound A into a small amount of deionized water, heating the mixture to 80 ℃, dropwise adding a mixed solution of concentrated HNO ₃/concentrated H ₂SO₄ into the solution, heating and refluxing for 1H, dropwise adding a mixed solution of concentrated HNO ₃/concentrated H ₂SO₄ again, continuing heating and refluxing reaction, gradually thickening and turning yellow, cooling after the reaction is finished, pouring the reaction solution into water, precipitating yellow precipitate, filtering, washing and drying, and recrystallizing the dried crude product in ethanol to obtain the pure compound B.

2) Uniformly mixing a compound B and a compound U in inert gas atmosphere, adding p-toluenesulfonic acid into the mixture, reacting at 140 ℃, cooling, adding deionized water into a reaction bottle, stirring for 0.5h, precipitating a crude product from the reaction mixture, filtering, drying to obtain a brown solid, and purifying the dried crude product through column chromatography to obtain a compound C;

The feeding mole ratio of the compound B to the different substituted phenols (compound U) is 1:2-10.

3) Under the atmosphere of inert gas, dissolving the compound C in dry acetone, dropwise adding triethylamine into the solution, stirring for 10min, dispersing the compound V into the dry acetone, dropwise adding the dry acetone into the reaction mixed solution in an ice bath, stirring at room temperature, adding ethyl acetate into the reaction solution after the reaction is finished, washing with water, drying, and performing column chromatography to obtain the compound D.

4) Dissolving the compound D in a mixed system of water/ethanol (volume ratio=1/3) in inert gas atmosphere, adding reduced Zn powder, ammonium chloride and glacial acetic acid, stirring for 4-6h at 50 ℃, carrying out suction filtration, extracting, drying and column chromatography to obtain a compound W,

The feeding molar ratio of the compound D to the reduced Zn powder is 1:6-15.

5) Under the atmosphere of inert gas, dissolving a compound W in dry and deoxidized nitrogen methyl pyrrolidone, adding different dibasic acid anhydrides (compound K) into the solution after the compound W is completely dissolved, reacting for more than 0.5h at 25 ℃, precipitating the reaction solution in a proper organic solvent, washing and drying to obtain different photosensitive polyamide acid PAA; adding triethylamine, pyridine and toluene into a solution of polyamide acid PAA in nitrogen methyl pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, precipitating, washing and drying the reaction solution in a proper organic solvent to obtain different photosensitive polyimide PSPI;

the feeding mole ratio of the compound Y to the different dibasic acid anhydrides (compound K) is 1:0.95-1.10.

The ratio of the two batches of concentrated HNO ₃/concentrated H ₂SO₄ in step 1 is 1:1.

The molar ratio of compound B to the differently substituted phenol (compound U) described in step 2 is preferably 1:2.5.

The feeding mole ratio of the compound D to the reduced Zn powder in the step 4 is preferably 1:12.

The molar ratio of compound W to dibasic acid anhydride (compound M) in step 5 is preferably 1:1.05.

The organic solvent in the step5 is selected from dichloromethane, ethyl acetate and ethanol.

The photo-crosslinkable photosensitive diamine monomer has good application effect in improving the property of polyimide.

The photosensitive polyimide prepared from the photo-crosslinkable photosensitive diamine monomer has good application prospect in photo-crosslinking and photo-curing materials.

The invention has the beneficial effects that: a novel photo-crosslinkable photosensitive material and application thereof are disclosed, wherein the photo-crosslinkable photosensitive diamine material takes spiro [ fluorene-9, 9' -xanthene ] as a core, two vertical non-conjugated units of fluorene ring and xanthene ring are provided with a three-dimensional large-volume steric hindrance rigid structure, and amino groups on the xanthene ring are connected with phenolic hydroxyl groups to enable the photo-crosslinkable diamine material to have photosensitivity. The two amino groups at the 2, 7-positions of the fluorene ring can be polymerized with different binary acid anhydrides to obtain the photo-crosslinkable photosensitive polyimide with good solubility, film forming property and thermodynamic stability, and the photo-crosslinkable photosensitive polyimide is used as a photo-crosslinking and photo-curing material and is expected to be applied to the fields of photoresist, three-dimensional printing and the like.

Drawings

FIG. 1 is a high resolution mass spectrum of a photo-crosslinkable diamine monomer W-1.

FIG. 2 is a chart showing nuclear magnetic resonance hydrogen spectrum of a photo-crosslinkable diamine monomer W-1.

FIG. 3 is a chart showing nuclear magnetic resonance spectroscopy of the photo-crosslinkable diamine monomer W-1.

FIG. 4 is a chart showing the Fourier infrared spectra of PAA-1 and PSPI-1.

FIG. 5 is a chart showing the characterization of Fourier infrared spectra before and after PSPI-1 UV irradiation.

Detailed Description

The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. It is intended that all those skilled in the art can make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof within the technical scope of the present invention disclosed in the present invention.

In the examples described below, the reagents used, unless otherwise specified, were prepared by conventional methods or purchased commercially.

Example 1

Synthetic route of photo-crosslinkable diamine monomer (W-1):

(1) Synthesis of intermediate B

A (2.00 g,11.10 mmol) was dispersed in 5ml deionized water under nitrogen atmosphere, the mixture was heated to 80℃and a mixture of concentrated HNO ₃ (65%, 6.92ml,99.89 mmol)/concentrated H ₂SO₄ (98%, 6.64ml,112.08 mmol) was added dropwise, and after refluxing for 1H, a mixture of concentrated HNO ₃ (65%, 6.92ml,99.89 mmol)/concentrated H ₂SO₄ (98%, 6.64ml,112.08 mmol) was added dropwise again, and the refluxing reaction was continued. After the TLC monitoring reaction is finished, the reaction liquid is cooled and poured into ice water to generate yellow precipitate, the yellow precipitate is filtered by suction, a filter cake is washed for 3 times and then is dried in vacuum, and the crude product obtained by drying is recrystallized in ethanol and is filtered by suction to obtain the compound B.

(2) Synthesis of intermediate C1

Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and resorcinol (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed and dried to a brown solid, and the dried crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C1 as a yellow solid;

(3) Synthesis of intermediate D1

Under nitrogen atmosphere, compound C1 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D1.

(4) Synthesis of diamine monomer W-1

Compound D1 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-1.

Mass spectrum and nuclear magnetic data of the compound W-1 are shown in fig. 1-3.

Example 2

Synthetic method referring to example 1, compound W-2 was synthesized with instead of/> .

Example 3

Synthetic method referring to example 1, compound W-3 was synthesized with instead of/> .

Example 4

The synthesis method of the compound B and the compound C1 is described in example 1.

(1) Synthesis of intermediate D4

Under nitrogen atmosphere, compound C1 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D4.

(2) Synthesis of diamine monomer W-4

Compound D4 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to obtain compound W-4. The product structure was identified by HRMS.

Example 5

Synthetic method referring to example 4, compound W-5 was synthesized with instead of/> .

Example 6

Synthetic method referring to example 4, compound W-6 was synthesized with instead of/> .

Example 7

Synthetic method referring to example 4, compound W-7 was synthesized with instead of/> .

Example 8

Synthetic method referring to example 4, compound W-8 was synthesized with instead of/> .

Example 9

Synthetic method referring to example 4, compound W-9 was synthesized with instead of/> .

Example 10

(1) Synthesis of intermediate B

(2) Synthesis of intermediate C2

In nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and hydroquinone (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, 15ml deionized water was added to the reaction flask, stirred for 0.5h, crude product was precipitated from the reaction mixture, was filtered off with suction, washed and dried to brown solid, and the dried crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C2 as yellow solid;

(3) Synthesis of intermediate D10

Under nitrogen atmosphere, compound C2 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D10.

(4) Synthesis of diamine monomer W-10

Compound D10 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-10. The product structure was identified by HRMS.

Example 11

Synthetic method referring to example 10, compound W-11 was synthesized with instead of/> .

Example 12

Synthetic method referring to example 10, compound W-12 was synthesized with instead of/> .

Example 13

The synthesis method of the compound B and the compound C2 is described in example 10.

(1) Synthesis of intermediate D13

Under nitrogen atmosphere, compound C2 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D13.

(2) Synthesis of diamine monomer W-13

Compound D13 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to obtain compound W-13. The product structure was identified by HRMS.

Example 14

Synthetic method referring to example 13, compound W-14 was synthesized using instead of/> .

Example 15

Synthetic method referring to example 13, compound W-15 was synthesized using instead of/> .

Example 16

Synthetic method referring to example 13, compound W-16 was synthesized using instead of/> .

Example 17

Synthetic method referring to example 13, compound W-17 was synthesized using instead of/> .

Example 18

Synthetic method referring to example 13, compound W-18 was synthesized using instead of/> .

Example 19

(1) Synthesis of intermediate B

(2) Synthesis of intermediate C3

Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and catechol (2.04 g,18.50 mmol) were mixed uniformly, p-toluenesulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, cooled, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed, dried to brown solid, and the dried crude product was separated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C3 as yellow solid;

(3) Synthesis of intermediate D19

Under nitrogen atmosphere, compound C3 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (468.62 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D19.

(4) Synthesis of diamine monomer W-19

Compound D19 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to give compound W-19. The product structure was identified by HRMS.

Example 20

Synthetic method referring to example 19, compound W-20 was synthesized with instead of/> .

Example 21

Synthetic method referring to example 19, compound W-21 was synthesized with instead of/> .

Example 22

The synthesis method of the compound B and the compound C3 is described in example 19.

(1) Synthesis of intermediate D22

Under nitrogen atmosphere, compound C3 (1.00 g,2.20 mmol) was dissolved in 8ml of dry acetone, triethylamine (672.99 ml,4.84 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (405.74 ml,4.84 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/petroleum ether system=1/1) to give compound D22.

(2) Synthesis of diamine monomer W-22

Compound D22 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.39 g,21.33 mmol), ammonium chloride (380.37 mg,7.11 mmol) and glacial acetic acid (101.68 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (ethyl acetate/petroleum ether system=2/1) to obtain compound W-22. The product structure was identified by HRMS.

Example 23

Synthetic method referring to example 23, compound W-23 was synthesized with instead of/> .

Example 24

Synthetic method referring to example 23, compound W-24 was synthesized with instead of/> .

Example 25

Synthetic method referring to example 23, compound W-25 was synthesized with instead of/> .

Example 26

Synthetic method referring to example 23, compound W-26 was synthesized with instead of/> .

Example 27

Synthetic method referring to example 23, compound W-27 was synthesized using instead of/> .

Example 28

Synthetic route of crosslinkable photosensitive diamine monomer (W-28):

(1) Synthesis of intermediate B

(2) Synthesis of intermediate C4

Under nitrogen atmosphere, compound B (2.00 g,7.40 mmol) and meta-aminophenol (2.02 g,18.50 mmol) were mixed uniformly, p-toluene sulfonic acid (2.55 g,14.80 mmol) was added to the mixture, dry powder was reacted at 140 ℃, after TLC monitoring the reaction was completed, cooled, 15ml deionized water was added to the reaction flask, stirred for 0.5h, the crude product was precipitated from the reaction mixture, filtered off with suction, washed, dried to a brown solid, and the dried crude product was separated and purified by column chromatography (methanol/dichloromethane system=1/50) to obtain compound C4 as a brown solid;

(3) Synthesis of intermediate D28

Under nitrogen atmosphere, compound C4 (1.00 g,2.21 mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92 mml,4.86 mmol) was added dropwise to the solution, after stirring for 10min, methacryloyl chloride (470.66 mml,4.86 mmol) was dispersed in 2ml of dry acetone, dropwise added to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/dichloromethane system=1/100) to give compound D28.

(4) Synthesis of diamine monomer W-31

Compound D28 (1.00 g,1.70 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.33 g,20.39 mmol), ammonium chloride (363.51 mg,6.80 mmol) and glacial acetic acid (97.17 mml,1.70 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered off while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/60) to give compound W-28. The product structure was identified by HRMS.

Example 29

Synthetic method referring to example 28, compound W-29 was synthesized with instead of/> .

Example 30

Synthetic method referring to example 28, compound W-30 was synthesized with instead of/> .

Example 31

The synthesis method of the compound B and the compound C4 is described in example 28.

(1) Synthesis of intermediate D31

Under nitrogen atmosphere, compound C4 (1.00 g,2.21 mmol) was dissolved in 8ml of dry acetone, triethylamine (675.92 ml,4.86 mmol) was added dropwise to the solution, after stirring for 10min, acryloyl chloride (407.50 ml,4.86 mmol) was dispersed in 2ml of dry acetone, dropwise added dropwise to the above reaction mixture under ice bath, a catalytic amount of DMAP was added to catalyze the reaction, stirring at room temperature, after TLC monitoring the end of the reaction, ethyl acetate was added to the reaction solution, washed with water, dried, and isolated and purified by column chromatography (ethyl acetate/dichloromethane system=1/100) to give compound D31.

(4) Synthesis of diamine monomer W-31

Compound D31 (1.00 g,1.78 mmol) was dissolved in a mixture of 4ml of water/ethanol (volume ratio=1/3) under a nitrogen atmosphere, reduced Zn powder (1.40 g,21.41 mmol), ammonium chloride (381.71 mg,7.14 mmol) and glacial acetic acid (102.03 mml,1.78 mmol) were added to the mixture, stirred at 50℃and after the completion of the TLC monitoring reaction, the mixture was filtered while hot, extracted and dried, and the crude product was isolated and purified by column chromatography (methanol/dichloromethane system=1/60) to obtain compound W-31. The product structure was identified by HRMS.

Example 32

Synthetic method referring to example 31, compound W-32 was synthesized with instead of/> .

Example 33

Synthetic method referring to example 31, compound W-33 was synthesized with instead of/> .

Example 34

Synthetic method referring to example 31, compound W-34 was synthesized with instead of/> .

Example 35

Synthetic method referring to example 31, compound W-35 was synthesized with instead of/> .

Example 36

Synthetic method referring to example 31, compound W-36 was synthesized with instead of/> .

Example 37

The synthesis of compound W-1 is described in example 1.

Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-1)

Under inert gas atmosphere, compound W-1 (100.00 mg,188.47 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, 3', 4' -benzophenone tetracarboxylic dianhydride (63.77 mg,197.90 mu mol) is added into the solution, stirred and reacted for 8 hours at 25 ℃, the reaction liquid is added into ethyl acetate in a dropwise manner, yellow matters are precipitated, washed and dried, and polyamide acid PAA-1 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-1 in azomethine pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-1.

Fourier infrared spectral data for PAA-1 and PSPI-1 are shown in FIG. 4. Comparing the curves of PAA-1 and PSPI-1, it can be seen that the 1363cm ^-1 is the telescopic vibration absorption peak of C-N bond on the imide ring, the 1783cm ^-1 and the 1731cm ^-1 are the symmetrical and asymmetrical telescopic vibration absorption peaks of 2 C=O on the imide ring, and the existence of the imide ring structure can be determined; the monomer W-1 has a methacrylate group, and a characteristic absorption peak of C=C in the methacrylate structure is clearly observed in a PSPI-1 map at 1608cm ^-1, so that the PSPI-1 can be determined to be prepared.

Example 38

Synthetic method referring to example 37, polymers PAA-2, PSPI-2 were synthesized.

Example 39

Synthetic method referring to example 37, polymers PAA-3, PSPI-3 were synthesized.

Example 40

Synthetic method referring to example 37, polymers PAA-4, PSPI-4 were synthesized.

Example 41

The synthesis of compound W-7 is described in example 7.

Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-5)

Under inert gas atmosphere, compound W-7 (100.00 mg,152.74 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, 2-bis (3, 4-dicarboxyphenyl) methane dianhydride (49.43 mg,160.37 mu mol) is added into the solution, stirring is carried out at 25 ℃ for 8 hours, the reaction solution is added into ethyl acetate in a dropwise manner, yellow matters are precipitated out, washing and drying are carried out, and polyamide acid PAA-5 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-5 in azomethyl pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-5.

Example 42

Synthetic method referring to example 41, polymers PAA-6, PSPI-6 were synthesized.

Example 43

Synthetic method referring to example 41, polymers PAA-7, PSPI-7 were synthesized.

Example 44

The synthesis of compound W-31 is described in example 31.

Synthetic route of photo-crosslinkable photosensitive polyimide (PSPI-8)

Under inert gas atmosphere, compound W-31 (100.00 mg,199.78 mu mol) is dissolved in 2ml of dry and deoxidized nitrogen methyl pyrrolidone, after complete dissolution, dibenzo dioxane dianhydride (68.01 mg,209.77 mu mol) is added into the solution, stirring reaction is carried out for 8 hours at 25 ℃, the reaction solution is added into ethyl acetate in a dropwise manner, yellow matters are precipitated, washing and drying are carried out, and polyamide acid PAA-8 is obtained; adding 0.5ml of triethylamine, 0.5ml of pyridine and 2ml of toluene into a solution of polyamide acid PAA-8 in azomethine pyrrolidone, dehydrating and cyclizing for 5 hours at 180 ℃, cooling, dripping the reaction solution into absolute ethyl alcohol to precipitate, washing and drying to obtain photo-crosslinkable photosensitive polyimide PSPI-8.

Example 45

Synthetic method referring to example 44, polymers PAA-9, PSPI-9 were synthesized.

Example 46

Synthetic method referring to example 44, polymers PAA-10, PSPI-10 were synthesized.

Example 47

Synthetic method referring to example 44, polymers PAA-11, PSPI-11 were synthesized.

Example 48

Synthetic method referring to example 44, polymers PAA-12, PSPI-12 were synthesized.

Example 49

30Mg of PSPI-1 was dissolved iN 0.2mL of dry DMAc, 5% of diphenyl- (2, 4, 6-trimethylbenzoyl) oxyphosphorus (photo-initiator TPO) was added, stirred at room temperature for 2h, a film was formed on a clean glass plate, the solvent was removed by drying, and a sample was taken for infrared spectroscopy (Nicolet iN10 micro-infrared spectrometer) after irradiation with 390nm ultraviolet light. Fig. 5 is an infrared spectrogram of the photo-crosslinkable polyimide PSPI-1 before and after ultraviolet irradiation, and compared with the photo-crosslinkable polyimide PSPI-1 before ultraviolet irradiation, the infrared characteristic absorption peak intensity of the c=c double bond of the photo-crosslinked Cl-PSPI-1 at the position 1606cm ^-1 is obviously weakened, which proves that the photo-crosslinking reaction occurs under ultraviolet irradiation.

Namely, it is shown that polyimide PSPI-1 can undergo photocrosslinking under ultraviolet irradiation.

Claims

1. A class of photo-crosslinkable photosensitive materials, characterized in that the materials have the structure of formula I, formula II or formula III:

Wherein X is each independently selected from n is a number greater than 1;

R ₁,R₂ is independently selected from m, each independently is an integer of 0-10, and R ₃ is C3-C8 cycloolefin;

y is each independently selected from

2. The photo-crosslinkable photosensitive material of claim 1, wherein X is each independently selected from the group consisting of

3. The photo-crosslinkable photosensitive material of claim 1, wherein R ₁,R₂ is independently selected from the group consisting of

4. Use of a photo-crosslinkable photosensitive material of formula I according to claim 1 for the preparation of a photo-crosslinkable polyimide.

5. Use of a photo-crosslinkable photosensitive material of formula I as claimed in claim 1 for the preparation of a photo-curable polyimide.