CN111909045A - End-capping agent containing crosslinkable group, modified polyimide precursor resin, photosensitive resin composition and application thereof - Google Patents

Abstract

The present invention provides an end capping agent containing a crosslinkable group, a modified polyimide precursor resin, a photosensitive resin composition and applications thereof. The end-capping agent containing a cross-linkable group of the present invention also acts as a cross-linking agent during high-temperature curing, and can be used in the synthesis of polyimide precursor resin to obtain a modified polyimide precursor with cross-linking function The modified polyimide precursor resin has the function of self-crosslinking and does not require an external crosslinking agent. During the high temperature curing process, the crosslinking group of the end capping agent can realize the crosslinking between the polyimide resin molecules. , forming a network cross-linked structure, thereby improving the overall heat resistance of the photoresist, and at the same time, it has the effects of improving the peeling resistance, reducing the amount of small molecule volatiles, and increasing the glass transition temperature of the photoresist. At the same time, since the crosslinkable group reacts with the phenolic hydroxyl group in the main chain of the polyimide, all or part of the hydroxyl group is consumed, which can reduce the hygroscopicity of the material, which is beneficial to improve the stability of the device.

Description

An end capping agent containing a crosslinkable group, a modified polyimide precursor resin, a light Sensitive resin composition and its application

technical field

The invention belongs to the technical field of photolithography, and relates to an end capping agent containing a crosslinkable group, a modified polyimide precursor resin, a photosensitive resin composition and applications thereof.

Background technique

Polyimide has excellent high and low temperature resistance, mechanical properties, dielectric properties, biocompatibility, low thermal expansion coefficient and many other properties, and is widely used in electronic equipment industry, aerospace industry, advanced composite materials, Fiber, engineering plastics, photoresist and other fields. Photosensitive polyimide is mainly used in photoresist in the field of microelectronics. Compared with ordinary polyimide, it can greatly simplify the lithography process, and because of its good heat resistance and mechanical properties , electrical properties and corrosion resistance and other characteristics, are widely used in large-scale integrated circuits and insulating spacers, surface passivation layers and ion implantation masks. At present, in order to ensure that the film layer of photosensitive polyimide has good performance under spin coating or slit coating process and avoid defects such as bubbles, it is required that the viscosity of the photoresist should not be too high, and the molecular weight of the corresponding polyimide resin is relatively high. Therefore, the thermal and mechanical properties of the resin itself are relatively large, and the molecular weight resin is poor. It is necessary to add a small molecular cross-linking agent to form a network cross-linked structure to improve its thermodynamic properties.

JP2014157297A discloses a photosensitive resin composition of polyimide. By introducing a cross-linking functional group containing a benzyl ether structure into the photosensitive resin composition, a cross-linked network structure is formed during high-temperature curing, so that the 5 The % heat loss temperature is increased, and it has good resistance to solvent stripping.

CN104730861A discloses a positive photosensitive resin composition, comprising: an alkali-soluble resin; a photosensitive diazoquinone compound; a crosslinking agent; a thermal acid generator; a phenolic compound; Including the crosslinking agent and the thermal acid generator in a weight ratio of 1, the positive photosensitive resin composition can be cured at a low temperature, maintain a front taper during thermal curing without pattern collapse, and be free from disintegration after heating and baking. A photosensitive resin film with little outgassing and excellent heat resistance and chemical resistance is generated in the coating layer. In addition, the photosensitive resin film has neither performance deterioration nor light emission defects such as black spots, pixel shrinkage, and the like due to degassing.

However, as mentioned above, in the prior art, the method of introducing a cross-linking agent has been used to increase the molecular weight of the resin and form a network structure to improve its physical properties. It is difficult to react completely, and there are residues; (2) the heat resistance of the crosslinking agent itself is poor, which will affect the thermal stability of the system, resulting in limited improvement of the thermal properties of the material, and at the same time lead to the increase of small molecule volatiles. As a result, the thermal stability, peel strength and mechanical properties of the photoresist are difficult to improve, and this problem has also become an urgent problem to be solved by those skilled in the art.

SUMMARY OF THE INVENTION

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a crosslinkable group-containing end-capping agent, a modified polyimide precursor resin, a photosensitive resin composition and uses thereof. The end-capping agent of the group can be used in the preparation of the modified polyimide precursor resin, so that the polyimide precursor itself has the cross-linking function, and no external cross-linking agent is required. The cross-linking group can realize the cross-linking between the polyimide resin molecules and form a network cross-linking structure, thereby improving the overall heat resistance of the photoresist, and at the same time, it can improve the peeling resistance, reduce the amount of small molecule volatiles, and improve the photolithography. Glass transition temperature and other effects.

For this purpose, the present invention adopts the following technical solutions:

In one aspect, the present invention provides a capping agent containing a crosslinkable group, and the capping agent containing a crosslinkable group has the structure shown in the following formula I:

且R¹、R²、R³、R⁴、R⁵和R⁶中至少一者选自-----C_xH_2xOH或

1≤x≤5，0≤i≤5，例如x可以为1、2、3、4或5，i可以为0、1、2、3、4或5；n为1-5的整数，例如1、2、3、4或5；wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from hydrogen atoms, halogen atoms, hydroxyl groups, -----C _x H _2xOH or

and at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is selected from -----C _x H _2xOH or

1≤x≤5, 0≤i≤5, for example x can be 1, 2, 3, 4 or 5, i can 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:

The dotted line represents the access position of the group.

The end-capping agent containing a cross-linkable group of the present invention also acts as a cross-linking agent during high-temperature curing, and can be used in the synthesis of polyimide precursor resin to obtain a modified polyimide precursor with cross-linking function body resin.

Preferably, at least one of said R ¹ , R ² and R ³ 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, and the modified polyimide precursor resin has the structure shown in the following formula II:

Wherein, R _a is any one of a C6-C30 aryl-containing organic group or a C3-C20 cycloalkyl group;

R _b is a C6-C30 aryl-containing organic group, a C2-C12 aliphatic hydrocarbon group, a C3-C20 cycloalkane group, a C2-C12 aliphatic hydrocarbon group containing Si in the main chain, or a Si-containing organic group The connected C6-C30 aromatic hydrocarbon group;

The p and q are each independently an integer from 0 to 4; when p and q are not zero, both (OH) _p and (OH) _q are directly connected to an aryl group, 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 and the like.

其中R¹、R²、R³、R⁴、R⁵和R⁶独立地选自氢原子、卤素原子、羟基、-----C_xH_2xOH或

且R¹、R²、R³、R⁴、R⁵和R⁶中至少一者选自-----C_xH_2xOH或

1≤x≤5，0≤i≤5，n为1-5的整数；R is

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from hydrogen atoms, halogen atoms, hydroxyl groups, -----C _x H _2xOH or

and at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is selected from -----C _x H _2xOH or

1≤x≤5, 0≤i≤5, n is an integer from 1 to 5;

A is any one of the following groups a-g:

代表取代基的接入位置。The dotted line in the structural formula of the substituent in the present invention

represents the access position of the substituent.

的可交联基团，使得改性聚酰亚胺前驱体树脂具有自交联功能，不需要外加交联剂，在高温亚胺化过程中，苄醇与酚羟基之间进行脱水成醚反应，或者苄基醚与酚羟基之间进行醚交换反应，聚合物主链间发生热交联反应，形成醚键，得到致密、稳定的交联网状结构，可以大幅提高光刻胶树脂的热稳定性、抗剥离性以及力学强度等性能，同时避免小分子交联剂的引入，可有效降低光刻胶小分子挥发物的溢出量。In the present invention, the modified polyimide precursor resin has an R group containing a crosslinkable group at the end, that is, containing -----C _x H _2xOH or

The crosslinkable group of the modified polyimide precursor resin makes the modified polyimide precursor resin have self-crosslinking function without the need for external crosslinking agent. During the high temperature imidization process, the dehydration reaction between benzyl alcohol and phenolic hydroxyl group is carried out , or the ether exchange reaction between the benzyl ether and the phenolic hydroxyl group, the thermal crosslinking reaction occurs between the polymer main chains to form ether bonds, resulting in a dense and stable cross-linked network structure, which can greatly improve the thermal stability of the photoresist resin. It can effectively reduce the overflow of small molecule volatiles in the photoresist.

At the same time, since the crosslinkable group reacts with the phenolic hydroxyl group in the main chain of the polyimide, all or part of the hydroxyl group is consumed, which can reduce the hygroscopicity of the material, which is beneficial to improve the stability of the device.

That is to say, in the present invention, the curing mechanism of the modified polyimide precursor resin is as follows:

a) Imination reaction: The amic acid (ester) group in the main chain of the polyamic acid resin precursor undergoes a cyclization reaction at high temperature to remove the small molecular compound (water or alcohol) to form a polyimide compound, and the reaction The formula is as follows:

b) Cross-linking reaction: the present invention utilizes the ether exchange reaction between benzyl ether and phenolic hydroxyl group or the dehydration reaction between benzyl alcohol and phenolic hydroxyl group to form ether to form a cross-linking connected by ether bonds between the main chains of polyimide Network structure, thereby improving the thermal and mechanical properties of the photoresist resin, anti-peeling properties, hygroscopicity and other indicators.

)的种类可以为一种也可以为多种，即在所述结构中并不单单表示只含有一种含羰基的结构单元，可以根据不同R_a和R_c的选择而在式II所示结构中含有多种含所示羰基的结构单元。同理，根据不同R_b的选择，在式II所示结构中也可以含有多种含氨基的结构单元(即

)。In the structure represented by formula II of the present invention, the structural unit containing R _a (that is,

) can be one _kind or many kinds, that is, in the structure, it does not simply mean that only one _carbonyl -containing structural unit is contained. Contains a variety of structural units containing the carbonyl group shown. Similarly, according to the selection of different R _b , the structure shown in formula II can also contain a variety of amino-containing structural units (that is,

).

等；所述以含Si的有机基团连接的C6～C30的芳香烃基中所述含Si的有机基团可以为含有Si的脂肪烃基或者含有-Si-O-基团的脂肪烃基，所述以含Si的有机基团连接的C12～C30的芳香烃基可以为

等。In the present invention, the C2-C12 aliphatic hydrocarbon group containing Si in the main chain means that there are Si atoms on the main chain of the aliphatic hydrocarbon group, for example, it can be

etc.; in the C6-C30 aromatic hydrocarbon group connected by the Si-containing organic group, the Si-containing organic group may be a Si-containing aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a -Si-O- group, the The C12-C30 aromatic hydrocarbon group connected with the Si-containing organic group can be

Wait.

等。In the present invention, the C6-C30 aryl-containing organic groups include aryl groups and groups formed by connecting aryl groups and other organic groups, and the C6-C30 aryl-containing organic groups are The attachment position of other groups can be on the aryl group or not on the aryl group, for example, it can be

Wait.

Preferably, the weight average molecular weight of the modified polyimide precursor resin is 2000-50000, such as 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, the R _a (OH) _p is selected from any one of the following groups:

The dotted line represents the access position of the group.

Preferably, the R _b (OH) _q is selected from any one of the following groups:

The dotted line represents the access position of the group.

Preferably, R is selected from any one of the following groups:

The dotted line represents the access position of the group.

In the present invention, among the C6-C30 aryl-containing organic groups, C6-C30 aromatic hydrocarbon groups, and C6-C30 aromatic hydrocarbon groups connected with Si-containing organic groups, C6-C30 represent carbon in the group The number of atoms, for example, can be 6, 8, 10, 15, 18, 20, 23, 26, 28, 30 carbon atoms, etc.; similarly, the number of carbon atoms in the C3-C20 cycloalkyl can be 3, 4, 5, 6, 8, 10, 13, 15, 18, 20, 22, 25, 28, 30 carbon atoms, etc., among the C2-C12 aliphatic hydrocarbon groups and the C2-C12 aliphatic hydrocarbon groups containing Si in the main chain C2 to C12 represent that the number of carbon atoms in the group may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12. Similarly, other limitations on the number of carbon atoms also mean that the number of carbon atoms in the group can be taken to any integer within the numerical range.

In a third aspect, the present invention provides a photosensitive resin composition comprising the modified polyimide precursor resin described in the second aspect.

Preferably, the photosensitive resin composition comprises the following components according to mass percentage:

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.%～20wt.%.

The mass percentage of the diazonaphthoquinone sulfonate is 1wt.%, 1.5wt.%, 2wt.%, 2.5wt.%, 3wt.%, 3.5wt.%, 4wt.%, 4.5wt.%, 5wt. %, 5.5 wt. %, 6 wt. %, 6.5 wt. %, 7 wt. % or 7.5 wt. % etc.

The mass percentage of the auxiliary agent is 0.02wt.%, 0.05wt.%, 0.08wt.%, 0.1wt.%, 0.15wt.%, 0.2wt.%, 0.25wt.%, 0.3wt.%, 0.35wt% %, 0.4wt.% or 0.45wt.% etc.

The mass percentage of the solvent is 61.5wt.%～95wt.%, such as 62wt.%, 65wt.%, 68wt.%, 70wt.%, 72wt.%, 75wt.%, 78wt.%, 80wt.%, 71wt.% %, 86wt.%, 88wt.%, 90wt.% or 94wt.% etc.

Preferably, the solid content of the photosensitive resin composition is 5wt.%˜38.5wt.%, such as 6wt.%, 8wt.%, 10wt.%, 15wt.%, 18wt.%, 20wt.%, 22wt.% , 25wt.%, 28wt.%, 30wt.%, 32wt.% or 36wt.%, etc., preferably 8wt.%～30wt.%.

In the present invention, the total content of each component in the photosensitive resin composition is 100 wt.%.

In the present invention, the solid content refers to the proportion of the sum of the mass of all substances in the photosensitive resin composition except the solvent in the composition.

In the present invention, the preferred solid content is 5wt.% to 38.5wt.%. Too low solid content will affect the film continuity and uniformity of the photosensitive resin composition during film formation, while too high solid content may lead to excessively high viscosity and thus lead to Problems such as air bubbles and poor flatness are generated during the coating process.

Preferably, the diazonaphthoquinone sulfonate is selected from any one or a combination of at least two of the following compounds:

r、s、t各自独立地选自0～5的整数，例如0、1、2、3、4或5；wherein D ₁ , D ₂ and D ₃ are each independently selected from -H or a DNQ group, the DNQ group being

r, s, and t are each independently selected from an integer from 0 to 5, such as 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 the PAC can form a hydrogen bond with the phenolic hydroxyl group, carboxyl group and other groups in the main chain of the photoresist resin, thereby inhibiting the resin in the photoresist. Solubility in alkaline solution, after exposure, the diazonaphthoquinone group reacts with water to generate indene acid, which makes the PAC compound easily soluble in dilute alkaline water, which improves the alkali dissolution rate in the exposed area, thereby obtaining the positive residue retained in the unexposed area. In the photolithography process, the reaction process of the diazonaphthoquinone group is as follows:

In the present invention, the adjuvant includes any one or a combination of at least two of a leveling agent, a coupling agent and a surfactant.

Preferably, the coupling agent is a siloxane group-containing coupling agent.

Preferably, the surfactant is a fluorosurfactant and/or a surfactant containing a polyethylene glycol structure.

In the present invention, the use of auxiliary agents helps to improve the flatness of the film, the adhesion between the photoresist compound and the substrate, and the reduction of residual film after development.

In the present invention, the solvent includes γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether formate, propylene glycol monoethyl ether formate, nitrogen methyl pyrrolidone, N, Any one or a combination of at least two of N-dimethylformamide or N,N-dimethylacetamide.

In a fourth aspect, the present invention provides an application of the photosensitive resin composition as described in the third aspect above in an OLED display panel;

Preferably, the photosensitive resin composition is used as a device protection material, an interlayer insulating material, a buffer layer material or a pixel segmentation layer material in OLED manufacturing.

Compared with the prior art, the present invention has the following beneficial effects:

The end-capping agent containing a cross-linkable group of the present invention also acts as a cross-linking agent during high-temperature curing, and can be used in the synthesis of polyimide precursor resin to obtain a modified polyimide precursor with cross-linking function body resin.

Since the modified polyimide precursor resin of the present invention contains a crosslinkable group, the modified polyimide precursor resin has a self-crosslinking function, and no external crosslinking agent is required. During the high temperature imidization process , dehydration into ether reaction between benzyl alcohol and phenolic hydroxyl group, or ether exchange reaction between benzyl ether and phenolic hydroxyl group, thermal cross-linking reaction occurs between polymer main chains to form ether bonds, resulting in dense and stable cross-linking The structure can greatly improve the thermal stability, peel resistance and mechanical strength of the photoresist resin, and at the same time avoid the introduction of small molecular crosslinking agents, which can effectively reduce the overflow of small molecular volatiles in the photoresist.

At the same time, because the crosslinkable group reacts with the phenolic hydroxyl group in the main chain of the polyimide, all or part of the hydroxyl group is consumed, the hygroscopicity of the material is reduced, and the stability of the device is improved.

Detailed ways

The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

Synthesis Example 1:

Synthesis of hydroxyl-containing dianhydride monomer 1:

Under nitrogen atmosphere, 10.8g (0.05mol) 3,3'-dihydroxy-4,4'-benzidine was dissolved in 50mL γ-butyrolactone, cooled to -15°C, and then 22.1g (0.105mol) ) 1,2,4-Trimellitic anhydride acid chloride was dissolved in 50mL of γ-butyrolactone, and the latter was added dropwise to the previous solution (the reaction was exothermic, the reaction temperature should be kept below -5°C during the dropwise addition), after the dropwise addition Continue to react for 5h. Most of the solvent was removed with a rotary evaporator, and the concentrate was poured into 300 mL of toluene for precipitation to obtain the corresponding hydroxyl-containing dianhydride monomer 1.

Structural characterization: method: Fourier transform infrared spectroscopy (the instrument used for Fourier transform infrared spectroscopy in the present invention is Spectrum One infrared spectrometer of Perkin Elmer company in the United States), characteristic peak: 1850cm ^-1 is the characteristic of acid anhydride group Peak, 3400cm ^-1 is the characteristic peak of -OH, and 1650cm ^-1 is the characteristic peak of amide group.

Synthesis Example 2:

Synthesis of hydroxyl-containing dianhydride monomer 2:

The difference from Preparation Example 1 is that 3,3'-dihydroxy-4,4'-benzidine is replaced with an equivalent amount of 5,5'-(1,4-phenylenebis(oxo)) Bis(2-aminophenol), the hydroxyl-containing dianhydride monomer 2 is obtained.

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: characteristic peak of acid anhydride group at 1850cm ^-1 , -OH characteristic peak at 3400cm ^-1 , characteristic peak of amide group at 1650cm ^-1 , characteristic peak of amide group at 1240cm ^-1 is the characteristic peak of aromatic COC.

Synthesis Example 3:

Synthesis of capping agents containing crosslinkable groups 1:

Take 1.39g (10mmol) m-nitrophenol, dissolve it in 20mL DMSO solvent, then add 1.18g (5mmol) p-dibromobenzene and 3.69g (22mmol) CsOH·H ₂ O, react under 150℃ oil bath for 36h, TLC tracking Reaction, after the reaction is complete, the product is purified by column chromatography to obtain Intermediate I;

Take 2.94g (10mmol) of Intermediate I, dissolve it in 20mL of DMSO solvent, then add 1.54g (10mmol) of 3,5-dimethylolphenol and 3.69g (22mmol) of CsOH·H ₂ O, react in an oil bath at 150°C 36h, the reaction was followed by TLC. After the reaction was completed, the product was purified by column chromatography to obtain intermediate II.

Take 0.72g (30mmol) of sodium hydride, add it to 20mL of dry anisole solution, take another 3.67g (10mmol) of intermediate II, add 30mL of dry anisole solvent, dropwise add it to the former solution, and reflux reaction after the dropwise addition After 2 h, 1.39 g (11 mmol) of dimethyl sulfate was added, and the reaction was refluxed overnight. After the reaction, the solution was washed with water, dried over anhydrous sodium sulfate, distilled under reduced pressure to remove the solvent, and purified by column chromatography to obtain Intermediate III;

Take 3.95g (10mmol) of intermediate III, add it into 50mL of DMF solvent, then add 2.13g (1mmol) of 5% palladium on carbon, stir the reaction under 0.4MPa hydrogen pressure for 24h, filter after the reaction, the filtrate is distilled to remove the solvent under reduced pressure, The amino-terminated agent 1 was obtained by purification by column chromatography.

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 4:

Synthesis of capping agent 2 containing crosslinkable groups:

The p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the crosslinkable group was replaced by m-dibromobenzene, and the m-nitrophenol was replaced by p-nitrophenol, and other reaction conditions were kept unchanged. End-Capping Agent 2 for Cross-Linking Groups:

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 5:

Synthesis of capping agent 3 containing crosslinkable groups:

The p-dibromobenzene used in the synthesis step of the end-capping agent 1 containing the cross-linkable group is replaced with mes-tribromobenzene, and other reaction conditions are kept unchanged to obtain the amino end-capping agent 3:

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 6:

Synthesis of capping agent 4 containing crosslinkable groups:

The p-dibromobenzene used in the synthesis step 1 of the end-capping agent containing a cross-linkable group was replaced with 1,2,4,5-tetrabromobenzene, and other reaction conditions were kept unchanged, and the following cross-linkable group was obtained. Capping agent 4 of the group:

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 7:

Synthesis of capping agents containing crosslinkable groups 5:

The p-dibromobenzene used in the synthesis step 1 of the end-capping agent containing a cross-linkable group was replaced by homo-3,3',5,5'-tetrabromobiphenyl, and other reaction conditions were kept unchanged to obtain a cross-linkable group. Binding group capping agent 5:

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 8:

Synthesis of capping agents containing crosslinkable groups 6:

The p-dibromobenzene used in the synthesis step 1 of the end-capping agent containing a crosslinkable group was replaced with 2,3,6,7-tetrabromonaphthalene, and other reaction conditions were kept unchanged to obtain a compound containing a crosslinkable group. End capping agent 6.

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: -NH ₂ characteristic peak at 3250cm ^-1 , methylene and methyl characteristic peaks at 2850cm ^-1 ～2950cm ^-1 , and aromatic at 1240cm ^-1 COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 9:

Synthesis of capping agent 7 containing crosslinkable groups:

Synthesis method: take 1.39g (10mmol) of m-nitrophenol, dissolve it in 20mL of DMSO solvent, then add 1.18g (5mmol) of m-dibromobenzene and 3.69g (22mmol) of CsOH·H ₂ O, and react in an oil bath at 150°C for 36h , TLC tracked the reaction, and after the reaction was complete, the product was purified by column chromatography to obtain Intermediate I;

Take 2.94g (10mmol) of Intermediate I, dissolve it in 20mL of DMSO solvent, then add 1.54g (10mmol) of 3,5-dimethylolphenol and 3.69g (22mmol) of CsOH·H ₂ O, react in an oil bath at 150°C 36h, the reaction was followed by TLC. After the reaction was completed, the product was purified by column chromatography to obtain intermediate II.

Take 3.67g (10mmol) of intermediate II, add it into 50mL of DMF solvent, then add 2.13g (1mmol) of 5% palladium on carbon, stir the reaction under 0.4MPa hydrogen pressure for 24h, filter after the reaction, the filtrate is distilled under reduced pressure to remove the solvent, The amino end-capping agent 7 was obtained by purification by column chromatography.

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: The broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak of -NH ₂ at 3250cm ^-1 and the characteristic peak of aromatic COC at 1240cm ^-1 .

Synthesis Example 10:

Synthesis of capping agents containing crosslinkable groups 8:

Synthesis method: replace the p-dibromobenzene used in the synthesis step 1 of the end-capping agent containing a crosslinkable group with 3,3',4,4',5,5'-hexabromobiphenyl, 3,5- Dimethylolphenol was replaced by 4-bromobenzyl alcohol, dimethyl sulfate was replaced by diethyl sulfate, and other reaction conditions were kept unchanged to obtain the end-capping agent containing crosslinkable groups 8

Structural characterization: Method: Fourier transform infrared spectrum, characteristic peaks: 3250cm ^-1 is -NH ₂ characteristic peak, 2850cm ^-1 ～2950cm ^-1 is methylene and methyl characteristic peaks, 1240cm ^-1 is aromatic COC characteristic peak, 1155cm ^-1 is the characteristic peak of fat COC.

Synthesis Example 11:

Synthesis of polyimide precursor 1:

Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add them into a 250mL there-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4°C. Another 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred and reacted for 3h, heated to 40°C, added 7.31g (20mmol) of end-capping agent 1, and stirred for 4h. , the temperature was raised to 50°C, and 9.53g (80mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50°C for 2h, the resulting solution was added to 1L of deionized water for precipitation. The obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain polyimide precursor 1 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 12

Synthesis of Modified Polyimide Precursors 2

The end-capping agent 1 in Synthesis Example 12 was replaced with an equivalent amount of the end-capping agent 2 to obtain a corresponding polyimide precursor 2 with a molecular weight of 7,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 13

Synthesis of Modified Polyimide Precursors 3

The end-capping agent 1 in Synthesis Example 12 was replaced with an equivalent amount of the end-capping agent 3 to obtain a corresponding polyimide precursor 3 with a molecular weight of 7,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 14

Synthesis of Modified Polyimide Precursors 4

The end-capping agent 1 in Synthesis Example 12 was replaced with an equivalent amount of the end-capping agent 4 to obtain a corresponding polyimide precursor 4 with a molecular weight of 7,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 15

Synthesis of Modified Polyimide Precursors 5

The end-capping agent 1 in Synthesis Example 12 was replaced with an equivalent amount of the end-capping agent 5 to obtain a corresponding polyimide precursor 5 with a molecular weight of 7,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 16

Synthesis of modified polyimide precursor 6:

Weigh 4.24g (15mmol) of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, put it into a 250mL there-necked flask, and put it in a nitrogen atmosphere. 50 mL of N-methylpyrrolidone (NMP) was added at 4°C, and the mixture was dissolved by mechanical stirring at 4°C. Another 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred and reacted for 3h, heated to 40°C, added 14.50g (20mmol) of end-capping agent 4, and stirred for 4h. , the temperature was raised to 50°C, and 9.53g (80mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50°C for 2h, the resulting solution was added to 1L of deionized water for precipitation. The obtained solid precipitate was vacuum-dried at 80° C. for 24 h to obtain polyimide precursor 6 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peaks: the broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak at 3400～3500cm ^-1 is the characteristic peak of -COOH, and the characteristic peak at 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -SO ₂ at 1150cm ^-1 .

Synthesis Example 17

Synthesis of modified polyimide precursor 7:

8.02 g (40 mmol) of 4,4'-diaminodiphenyl ether was added to a 250 mL three-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and it was dissolved by mechanical stirring at 4°C. In addition, 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred for 3 hours, heated to 40°C, added with 14.50g (20mmol) of amino end-capping agent 4, and stirred for reaction 4h, the temperature was raised to 50°C, and 9.53g (80mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50°C for 2h, the resulting solution was added to 1L of deionized water for precipitation. , the obtained solid precipitate was vacuum-dried at 80 °C for 24 h to obtain polyimide precursor 7 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peaks: the broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak at 3400～3500cm ^-1 is the characteristic peak of -COOH, and the characteristic peak at 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 and the characteristic peak of -CO in -CONH at 1650cm ^-1 .

Synthesis Example 18

Synthesis of modified polyimide precursor 8:

Weigh 4.24g (15mmol) of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, put it into a 250mL there-necked flask, and put it in a nitrogen atmosphere. 50 mL of N-methylpyrrolidone (NMP) was added at 4°C, and the mixture was dissolved by mechanical stirring at 4°C. Another 15.51 g (50 mmol) of 4,4'-diphenyl ether tetracarboxylic dianhydride was weighed and mixed with 35 mL of NMP, quickly added to the reaction system, stirred and reacted for 3 h, heated to 40 ° C, and 14.50 g (20 mmol) of amino end capping was added. Agent 4, stirred for 4 hours, heated to 50 °C, slowly added 9.53 g (80 mmol) of N,N-dimethylformamide dimethyl acetal dropwise to the reaction system, reacted at 50 °C for 2 hours, and added the resulting solution to the Precipitation in 1 L of deionized water, and the obtained solid precipitate was vacuum-dried at 80° C. for 24 h to obtain polyimide precursor 8 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peaks: the broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak at 3400～3500cm ^-1 is the characteristic peak of -COOH, and the characteristic peak at 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -SO ₂ at 1150cm ^-1 .

Synthesis Example 19

Synthesis of Modified Polyimide Precursors 9

Synthesis method: Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add 250mL of three In the bottle, 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the solution was dissolved by mechanical stirring at 4°C. Another 35.0g (52mmol) of hydroxyl-containing dianhydride monomer 2 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred and reacted for 3h, then heated to 40°C, added with 17.4g (24mmol) of end-capping agent 4, and stirred for 4h. , the temperature was raised to 50 °C, and 9.91 g (83.2 mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50 °C for 2 h, the resulting solution was added to 1 L of deionized water for precipitation. , the obtained solid precipitate was vacuum-dried at 80°C for 24h to obtain polyimide precursor 9 with a molecular weight of 5000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 20

Synthesis of Modified Polyimide Precursors 10

Synthesis method: Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add 250mL of three In the bottle, 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the solution was dissolved by mechanical stirring at 4°C. In addition, 28.2g (42mmol) of hydroxyl-containing dianhydride monomer 2 was weighed and mixed with 35mL of NMP, and added to the reaction system in two times. After stirring for 3h, the temperature was raised to 40°C, 3.1g (4mmol) of end-capping agent 6 was added, and the mixture was stirred. The reaction was carried out for 4 h, the temperature was raised to 50 °C, and 8.0 g (67.2 mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After 2 h of reaction at 50 °C, the resulting solution was added to 1 L of deionized water. Precipitation in water, and the obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain polyimide precursor 10 with a molecular weight of 30,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 21

Synthesis of Modified Polyimide Precursors 11

Synthesis method: Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add 250mL of three In the bottle, 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the solution was dissolved by mechanical stirring at 4°C. Another 53.8g (80mmol) of hydroxyl-containing dianhydride monomer 2 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred for 3h, heated to 40°C, added with 27.0g (80mmol) of end capping agent 7, and stirred for 4h. , the temperature was raised to 50°C, and 15.2g (128mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50°C for 2h, the resulting solution was added to 1L of deionized water for precipitation. The obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain a polyimide precursor 11 with a molecular weight of 2000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 22

Synthesis of Polyimide Precursors 12

Synthetic method Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add 250mL there-necked flask 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4°C. In addition, 27.1g (40.4mmol) of hydroxyl-containing dianhydride monomer 2 was weighed and mixed with 35mL of NMP, added to the reaction system in two times, and after stirring for 3h, the temperature was raised to 40°C, and 0.81g (0.8mmol) of end-capping agent 8 was added. , stirred and reacted for 4 h, heated to 50 °C, slowly added 8.0 g (67.2 mmol) of N,N-dimethylformamide dimethyl acetal dropwise to the reaction system, reacted at 50 °C for 2 h, and added 1 L of the resulting solution Precipitation in deionized water, and the obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain polyimide precursor 12 with a molecular weight of 50,000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Synthesis Example 23

Synthesis of modified polyimide precursor 13:

Weigh 4.24g (15mmol) 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 2.85g (25mmol) 1,4-cyclohexanediamine (TCI, CAS: 3114-70-3) , was added into a 250 mL three-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4°C. Another 11.21g (50mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (TCI, CAS: 2754-41-8) was weighed and mixed with 35mL of NMP, quickly added to the reaction system, and after stirring for 3h, The temperature was raised to 40°C, 14.50g (20mmol) of amino end-capping agent 4 was added, the reaction was stirred for 4h, the temperature was raised to 50°C, and 9.53g (80mmol) of N,N-dimethylformamide dimethyl was slowly added dropwise to the reaction system. The acetal was reacted at 50°C for 2h, the obtained solution was added to 1L of deionized water for precipitation, and the obtained solid precipitate was vacuum-dried at 80°C for 24h to obtain polyimide precursor 13 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peaks: the broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak at 3400～3500cm ^-1 is the characteristic peak of -COOH, and the characteristic peak at 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -SO ₂ at 1150cm ^-1 .

Synthesis Example 24

Synthesis of modified polyimide precursor 14:

Weigh 1.74g (15mmol) 1,6-hexanediamine (Bailingwei, CAS: 124-09-4), 6.21g (25mmol) 1,3-bis(3-aminopropyl)-1,1',3 , 3'-tetramethyldisiloxane (TCI, CAS: 2469-55-8) was added to a 250 mL three-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and it was dissolved by mechanical stirring at 4°C. Another 33.6g (50mmol) of hydroxyl-containing dianhydride monomer 2 was weighed, mixed with 35mL of NMP, quickly added to the reaction system, stirred for 3h, heated to 40°C, added with 14.50g (20mmol) of amino end-capping agent 4, stirred The reaction was carried out for 4 h, the temperature was raised to 50 °C, and 9.53 g (80 mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After 2 h of reaction at 50 °C, the resulting solution was added to 1 L of deionized water. Precipitation, the obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain polyimide precursor 14 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peaks: the broad peak at 3200～3400cm ^-1 is the characteristic peak of -OH, the characteristic peak at 3400～3500cm ^-1 is the characteristic peak of -COOH, and the characteristic peak at 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in the carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , the characteristic peak of -Si-O at 1020cm ^-1 , and the characteristic peak at 800cm ^-1 is the characteristic peak of -Si-C.

Synthesis Example 25

Synthesis of Modified Polyimide Precursors 15

Synthesis method: Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.86g (25mmol) of bis(4-aminophenoxy)dimethylsilane ( Bailingwei, CAS: 1223-16-1), was added into a 250 mL three-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under a nitrogen atmosphere, and the solution was dissolved by mechanical stirring at 4°C. Another 33.6g (50mmol) of hydroxyl-containing dianhydride monomer 2 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred and reacted for 3h, heated to 40°C, added 14.5g (20mmol) of end-capping agent 4, and stirred for 4h. , the temperature was raised to 50°C, and 9.53g (80mmol) of N,N-dimethylformamide dimethyl acetal was slowly added dropwise to the reaction system. After reacting at 50°C for 2h, the resulting solution was added to 1L of deionized water for precipitation. The obtained solid precipitate was vacuum-dried at 80° C. for 24 hours to obtain polyimide precursor 15 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 is the characteristic peak of -CO in -CONH at 1650cm ^-1 , the characteristic peak of -CF at 1350cm ^-1 is the characteristic peak of -CF ₃ at 1020cm ^-1 It is the characteristic peak of -Si-O, and the characteristic peak of -Si-C at 800cm ^-1 .

Comparative Synthesis Example 1:

Synthesis of unmodified polyimide precursor 1:

Weigh 5.49g (15mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 5.01g (25mmol) of 4,4'-diaminodiphenyl ether, add them into a 250mL there-necked flask, 50 mL of N-methylpyrrolidone (NMP) was added under nitrogen atmosphere, and the mixture was dissolved by mechanical stirring at 4°C. Another 28.2g (50mmol) of hydroxyl-containing dianhydride monomer 1 was weighed and mixed with 35mL of NMP, quickly added to the reaction system, stirred for 3h, heated to 40°C, added 1.86g (20mmol) of aniline, stirred for 4h, and heated to 50°C, slowly add 9.53g (80mmol) N,N-dimethylformamide dimethyl acetal dropwise to the reaction system, react at 50°C for 2h, add the obtained solution to 1L of deionized water, add the obtained solution to Precipitation in 1 L of deionized water, and the obtained solid precipitate was vacuum-dried at 80° C. for 24 h to obtain unmodified polyimide precursor 1 with a molecular weight of 7000.

Structural characterization: Method: Fourier transform infrared spectroscopy, characteristic peak: 3400～3500cm ^-1 characteristic peak is -COOH characteristic peak, 3200～3400cm ^-1 broad peak is -OH characteristic peak, 2850cm ^-1 ～2950cm ^-1 It is the characteristic peak of methylene and methyl group, the characteristic peak of -CO in carboxyl group at 1720cm ^-1 , the characteristic peak of -CO in -CONH at 1650cm ^-1 , and the characteristic peak of -CF ₃ at 1350cm ^-1 .

Example 1

The present embodiment provides a photosensitive resin composition, prepared by the following method:

Weigh 5g of modified polyimide precursor resin 1, dissolve it in 50mL of mixed solvent consisting of 40% γ-butyrolactone, 20% ethyl lactate, 40% propylene glycol monomethyl ether, add 1g PAC-1 , 0.01g silane coupling agent, 0.02g fluorine-containing surfactant, after stirring and dissolving, filter through 0.45 micron filter to obtain photosensitive polyimide resin composition 1.

Example 2

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 2 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 2.

Example 3

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 3 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 3.

Example 4

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 4 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 4.

Example 5

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 5 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 5.

Example 6

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 6 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 6.

Example 7

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 7 of the same quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 7.

Example 8

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 8 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 8.

Example 9

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 9 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 9.

Example 10

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 10 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 10.

Example 11

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 11 of equal quality, and the photosensitive polymer is prepared in the same way. Imide resin composition 11.

Example 12

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 12 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 12.

Example 13

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 13 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 13.

Example 14

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 12 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 14.

Example 15

This embodiment provides a photosensitive resin composition, which is different from Embodiment 1 in that the modified polyimide precursor 1 is replaced with a modified polyimide precursor 12 of equal quality, and the photosensitive polymer is prepared by the same method. Imide resin composition 15.

Comparative Example 1

The difference from Example 1 is that the modified polyimide precursor 1 is replaced with an unmodified polyimide precursor 1 of the same quality 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 the same quality, and 1.0 g of the end capping agent 4 containing crosslinkable groups was added as Crosslinking agent to obtain photosensitive resin composition D2.

Lithography performance test:

The prepared photosensitive polyimide resin composition was spin-coated on a 5-inch square glass substrate, pre-baked at 120 °C for 180 s to remove most of the solvent, and then exposed under a 365 nm UV exposure machine with 2.38% tetramethylene Base on ammonium hydroxide (2.38wt.% TMAH) development, the development time is 60s～120s, the photolithography pattern is obtained, and the sensitivity is the minimum exposure amount required to show the complete pattern within the development time of 60s.

Outgas (small molecule volatilization) test:

Sample preparation: The prepared photosensitive resin composition was spin-coated (note: the samples of Examples 10, 12 and Comparative Example 2 had high molecular weight and high viscosity, so the glue coating speed was adjusted to 1000 rpm, and the samples of Example 11 were The molecular weight of the sample is small, the viscosity is low, the rotating speed is adjusted to 200 rpm, and the other examples and comparative examples are coated on a 5-inch square glass substrate by the method of rotating at 250 rpm, and pre-baked at 120 ° C for 180 s for After removing most of the solvent, the film-coated glass substrate was placed in a 250°C clean oven under nitrogen protection (oxygen concentration <500ppm) for 1 hour, and the film was scraped off and vacuum-sealed for later use.

Thermogravimetric analysis test: Test atmosphere: nitrogen, heating program: 40°C for 30min, then heat up to 250°C at a rate of 5K/min, hold for 30min, and calculate the mass loss during the 250°C heat preservation.

Anti-peeling performance 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 °C for 180 s to remove most of the solvent, and the film thickness t was measured. Place in a nitrogen clean oven at 250°C (oxygen concentration <500ppm) for 1 hour, and test the film thickness t ₁ with an ellipsometer. Immerse the coated glass substrate in TOK106 stripping solution at 65℃ for 150s, take out and rinse with deionized water, then bake in a nitrogen clean oven (oxygen concentration <500ppm) at 230℃ for 30min, and test the film thickness with an ellipsometer t ₂ , calculate the film thickness change Δt=t ₂ −t ₁ before and after etching.

The above performance test results are shown in Table 1.

Table 1

Mechanical property test:

Pour the photosensitive resin composition into a mold of 150mm*10mm*0.5mm (length*width*depth), place it on a water platform, air it to semi-dry at room temperature, and place it in a nitrogen oven. -130°C (30min) - 150°C (30min) - 200°C (30min) - 250°C (60min) - After curing by the temperature program of natural cooling to room temperature, a standard test strip is obtained, the film thickness is 20μm, The mechanical properties were tested with a universal material testing machine, the displacement rate was 5mm/min, the environment was 23°C, and the humidity was 50±5%.

The mechanical properties test results 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

According to the data analysis of Table 1 and Table 2, compared with Comparative Example 1 without cross-linking function, the polyimide precursor photosensitive resin composition with cross-linking function prepared by the present invention has good photolithography performance, resistance to Thermal properties, mechanical properties, low small molecule volatiles (outgas) and other comprehensive properties have excellent application potential. It can be seen from the examples in the comparison table that the density and content of the cross-linking groups have a greater impact on the comprehensive performance of the photoresist, and the end-capping agent containing more cross-linking groups is used, and the cross-linking site ( The higher the density of hydroxyl groups, the more favorable it is for the polyimide resin to form a body-shaped cross-linked structure during the curing process, improve the anti-peeling performance of the resin, and reduce the resin outgas.

If an end-capping agent containing a crosslinkable group is added as a small molecule component in the photosensitive resin composition (ie, Comparative Example 2), the anti-peeling performance can also be significantly improved and the outgas can be reduced, but the effect is more direct than the corresponding structure. The resin synthesized by the amino-terminating agent is poor. However, Comparative Example 2, which has no cross-linking effect, can still greatly improve the overall properties of the resin, such as heat resistance, mechanical properties, and low outgas.

The applicant declares that the present invention illustrates the crosslinkable group-containing end capping agent, modified polyimide precursor resin, photosensitive resin composition and application thereof by the above examples, but the present invention is not limited to For the above-mentioned embodiments, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (10)

1. an end-capping agent containing a cross-linkable group is characterized in that, the described end-capping agent containing a cross-linkable group has the structure shown in the following formula I:

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from hydrogen atoms, halogen atoms, hydroxyl groups,

and at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is selected from

1≤x≤5, 0≤i≤5; n is an integer from 1 to 5; A is any one of the following groups a-g:

The dotted line represents the access position of the group. 2. The end-capping agent containing a crosslinkable group according to claim 1, wherein at least one of the R ¹ , R ² and R ³ is selected from -CH ₂ OH, -CH ₂ OCH ₃ or -CH ₂ OCH ₂ CH ₃ . 3. The end-capping agent containing a cross-linkable group according to claim 1, wherein the end-capping agent containing a cross-linkable group is any one of the following compounds:

4. A modified polyimide precursor resin is characterized in that, the modified polyimide precursor resin has the structure shown in the following formula II:

Wherein, R _a is any one of a C6-C30 aryl-containing organic group or a C3-C20 cycloalkyl group; R _b is a C6-C30 aryl-containing organic group, a C2-C12 aliphatic hydrocarbon group, a C3-C20 cycloalkyl group, a C2-C12 aliphatic hydrocarbon group containing Si in the main chain, or a Si-containing organic group The connected C6-C30 aromatic hydrocarbon group; The p and q are each independently an integer from 0 to 4; when p and q are not zero, both (OH) _p and (OH) _q are directly connected to an aryl group, and p and q are not 0 at the same time; R _c is a hydrogen atom or an alkyl group of C1-C8; m≥2; R is

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are independently selected from hydrogen atoms, halogen atoms, hydroxyl groups,

and at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is selected from

1≤x≤5, 0≤i≤5, n is an integer from 1 to 5; A is any one of the following groups a-g:

The dotted line represents the access position of the group. 5 . The modified polyimide precursor resin according to claim 4 , wherein the weight average molecular weight of the modified polyimide precursor resin is 2000-50000, preferably 5000-30000. 6 . 6. The modified polyimide precursor resin according to claim 4, wherein the R _a (OH) _p is selected from any one of the following groups:

The dotted line represents the access position of the group. 7. modified polyimide precursor resin according to claim 4, is characterized in that, described R _b (OH) _q is selected from any one in following group:

The dotted line represents the access position of the group. 8. modified polyimide precursor resin according to claim 4, is characterized in that, R is selected from any one in following group:

The dotted line represents the access position of the group. 9. A photosensitive resin composition, characterized in that the photosensitive resin composition comprises the modified polyimide precursor resin according to any one of claims 4-8; Preferably, the solid content of the photosensitive resin composition is 5wt.%˜38.5wt.%, preferably 8wt.%˜30wt.%. 10. The application of the photosensitive resin composition according to claim 9 in an OLED display panel; Preferably, the photosensitive resin composition is used as a device protection material, an interlayer insulating material, a buffer layer material or a pixel segmentation layer material in OLED manufacturing.