A kind of nitrogen heterocyclic polysiloxane and its preparation method and application

Abstract

The invention discloses a nitrogen-heterocyclic polysiloxane and a preparation method and application thereof. The nitrogen-heterocyclic polysiloxane can significantly enhance the thermal stability, mechanical properties and chemical resistance of a cured film of a heat-resistant resin after high-temperature thermal curing, and enhance the adhesion between the heat-resistant resin and a substrate.

Description

Technical Field

[0001] The invention relates to a nitrogen-containing heterocyclic polysiloxane and a preparation method and application thereof, belonging to the technical field of organosilicon compounds. Background Art

[0002] Polysiloxane is a polymer with a highly branched structure, which has a large number of modifiable functional groups and has excellent properties such as low viscosity and high fluidity. In addition, hyperbranched polymers are generally prepared in a one-step or quasi-one-step process, which is more industrially practical than dendritic polymers that use a multi-step synthesis process to achieve a perfectly symmetrical structure. Hyperbranched polysiloxane is a hyperbranched polymer with Si-O-Si as the main chain. It has both the stability of inorganic substances and the excellent properties of hyperbranched polymers, and is widely used as a modified additive for fibers and resins.

[0003] In recent years, heat-resistant resins such as polyimide (PI), polybenzoxazole (PBO), polyamide, and polythiazole have been widely used as cured films such as insulating films, phase difference films, and optical characteristic films in optical electronic components such as liquid crystal display elements, organic EL display elements, and integrated circuit elements due to their excellent performance. The film cured by heating will exist in the device as a permanent film, so the performance of the cured film after heating is very important. In order to ensure the reliability of semiconductor packaging, the adhesion between the cured film and the surface material of the semiconductor chip, the mechanical properties of the film, and the chemical resistance are very important. Summary of the invention

[0004] The purpose of the present invention is to provide a nitrogen-containing heterocyclic polysiloxane having a special nitrogen heterocyclic structure, which can significantly enhance the thermal stability, mechanical properties, and chemical resistance of a cured film of a heat-resistant resin after high-temperature (above 300° C.) thermal curing, and enhance the adhesion between the heat-resistant resin and the substrate.

[0005] According to the first aspect of the present application, a nitrogen-containing heterocyclic polysiloxane is provided. The nitrogen-containing heterocyclic polysiloxane has a structural formula shown in the following general formula (1):

[0006]

[0007] Furthermore, in the above formula (1), Y is a nitrogen-containing heterocyclic organic group. Specifically, Y can be selected from one, two or more structures shown in the following formulas (2) to (5), and * represents an insertion site:

[0008]

[0009] Furthermore, in the above formulae (2) to (5), R1 is selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Specifically, the alkyl group or alkoxy group having 1 to 20 carbon atoms may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., and may be an alkoxy group such as hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, etc. Preferably, R1 is selected from a hydrogen atom, methyl, ethyl, butyl, hydroxyethyl methacrylate.

[0010] Furthermore, in the above formulae (2) to (5), the W group is selected from a nitrogen-containing heterocyclic structure, such as a structure containing a triazole group, a tetrazolyl group, a triazine group, an imidazole group, an oxazolyl group, etc.;

[0011] Preferably, W is at least one of the structures ①, ②, and ③ in the following formula (6), and * represents an insertion site:

[0012]

[0013] In formula (6), R2, R3, R4, R5, and R6 are independently selected from at least one of a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group having 1 to 10 carbon atoms may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, or a cycloalkyl group such as cyclopentyl and cyclohexyl, or an aromatic group such as phenyl and tolyl, or an aralkyl group such as benzyl, phenethyl, and phenylpropyl, or an unsaturated alkenyl group such as vinyl, allyl, butenyl, propenyl, isopropenyl, and phenylalkenyl.

[0014] Preferably, R2, R3, R4, R5, and R6 are independently selected from a hydrogen atom and a saturated alkyl group having 1 to 3 carbon atoms; more preferably, R2, R3, R4, R5, and R6 are independently selected from a hydrogen atom, a methyl group, and an ethyl group.

[0015] According to the second aspect of the present application, the present invention provides a method for preparing the above-mentioned nitrogen-containing heterocyclic polysiloxane. The method comprises the following steps:

[0016] Step 1, under gas protection, stirring and mixing the organic solvent, nitrogen-containing heterocyclic silane coupling agent monomer and catalyst;

[0017] Step 2, controlling the temperature of the mixture in step 1 at 0-40°C, adding water dropwise thereto, keeping the mixture warm for reaction after the addition is complete, and then raising the temperature to 50-100°C to continue the reaction;

[0018] Step 3: After the reaction, the organic layer is separated and the volatiles are removed by distillation to obtain a nitrogen-containing heterocyclic polysiloxane.

[0019] Furthermore, in step 1, the nitrogen-containing heterocyclic silane coupling agent monomer is selected from at least one of the structures represented by the following formula (7):

[0020]

[0021] In formula (7), the definitions of R1 and W are consistent with the above definitions.

[0022] In formula (7), R7 is selected from a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., or a cycloalkyl group such as cyclopentyl, cyclohexyl, etc., or an aromatic group such as phenyl, tolyl, etc., or an aralkyl group such as benzyl, phenethyl, phenylpropyl, etc., or an unsaturated alkenyl group such as vinyl, allyl, butenyl, propenyl, isopropenyl, phenylalkenyl, etc. Preferably, R7 is a saturated alkyl group having 1 to 10 carbon atoms, and more preferably, R7 is methyl or ethyl.

[0023] Furthermore, when the W group is When the nitrogen-containing heterocyclic silane coupling agent monomer represented by formula (7) is prepared by referring to the preparation method in patent ZL202111145299.6.

[0024] Furthermore, when the W group is When, the preparation method of the nitrogen-containing heterocyclic silane coupling agent monomer shown in formula (7) is:

[0025] Category 1: Amide-based nitrogen-containing heterocyclic silane coupling agent monomers:

[0026] The oxazole diamine or imidazole diamine is mixed with a solvent, and then the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride is slowly added in an amount twice the molar amount of the diamine. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours. After the reaction is completed, the nitrogen-containing heterocyclic silane coupling agent monomer of the amic acid type is obtained by distillation under reduced pressure and purification.

[0027] The second category: imide nitrogen-containing heterocyclic silane coupling agent monomer:

[0028] The oxazole diamine or imidazole diamine is mixed with a solvent, and then the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride is slowly added in a molar amount twice that of the diamine. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours, and then a base and anhydride are added to the reaction system for imidization. After the reaction is completed, the solvent, unreacted raw materials and by-products in the system are removed by reduced pressure distillation to obtain an imide-type nitrogen-containing heterocyclic silane coupling agent monomer.

[0029] Category 3: Amide ester nitrogen-containing heterocyclic silane coupling agent monomers:

[0030] The oxazole diamine or imidazole diamine is mixed with a solvent, and then the silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride is slowly added in a molar amount twice that of the diamine. After the addition is completed, the reaction is continued at 23-26° C. for 20-22 hours, and then an esterification agent (N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, etc.) is added to the system for esterification reaction. After the reaction is completed, it is distilled under reduced pressure to obtain an amide ester nitrogen-containing heterocyclic silane coupling agent monomer.

[0031] Optionally, in step 1, the organic solvent is selected from at least one of hydrocarbons, ketones, esters, ethers, and alcohols. The hydrocarbons include, for example, toluene and xylene; the ketones include, for example, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone, etc.; the esters include, for example, ethyl acetate, n-butyl acetate, isopentyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, etc.; the ethers include, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc.; the alcohols include, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, etc. The organic solvent is preferably one that is immiscible with water, and these organic solvents may be used alone or in combination of two or more.

[0032] Optionally, in step 1, the catalyst may be one of an acid, an alkali metal compound, an organic base, and the like. Examples of the acid include hydrochloric acid, p-toluenesulfonic acid, and the like; examples of the alkali metal compound include, for example, sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, and the like; examples of the organic base include, for example, primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazacycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide are preferred.

[0033] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the organic solvent is 1:0.5-20, for example, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, preferably 1:1-10.

[0034] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the catalyst is 1:0.01 to 0.3, for example, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, preferably 1:0.01 to 0.1.

[0035] Optionally, in step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:1-50, for example, 1:1, 1:2, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, preferably 1:2-20.

[0036] Optionally, in step 2, the water is added dropwise for 0.5 to 5 h, for example, 0.5 h, 1 h, 2 h, 3 h, 4 h, or 5 h.

[0037] Optionally, in step 2, water is added dropwise at 0-40°C, and the temperature can be 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C. After the water is added dropwise, the reaction is kept warm for 3-6 hours, such as 3 hours, 4 hours, 5 hours, 6 hours. After the reaction, the temperature is continued to rise to 50-100°C, such as 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, and the reaction is continued at this temperature for 6-12 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours.

[0038] According to the third aspect of the present application, the present invention provides the use of the above-mentioned nitrogen-containing heterocyclic polysiloxane as a heat-resistant resin modifier. The nitrogen-containing heterocyclic polysiloxane provided by the present invention can be used as a modifier for a heat-resistant resin to enhance the adhesion between the heat-resistant resin and the substrate, and can also enhance the thermal stability, mechanical properties and chemical resistance of the heat-resistant resin.

[0039] Optionally, the heat-resistant resin includes at least one of polyimide resin, polyimide precursor, polybenzoxazole resin, polybenzoxazole precursor, polyamide resin, polyamide-imide resin, polybenzimidazole resin, and polybenzothiazole resin. The heat-resistant resin can be directly purchased from the market, or prepared by a method disclosed in the prior art, which is not difficult for those skilled in the art.

[0040] Optionally, the polyimide precursor is selected from polyamic acid or polyamic acid ester.

[0041] Optionally, the polybenzoxazole precursor is selected from polyhydroxyamides.

[0042] Optionally, the amount of the nitrogen-containing heterocyclic polysiloxane is 0.1 to 20% of the mass of the heat-resistant resin, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18%, 20%, preferably 1 to 10%.

[0043] Optionally, the nitrogen-containing heterocyclic polysiloxane may be one type, or two or more types.

[0044] The present invention independently develops a polysiloxane containing a special nitrogen heterocyclic structure, and the polysiloxane containing a nitrogen heterocyclic structure can be used as a modifier for heat-resistant resins, and can significantly enhance the adhesion of the heat-resistant resin to the substrate after high-temperature thermal curing, and significantly improve the thermal stability, mechanical properties and chemical resistance of the cured film formed by high-temperature thermal curing of the heat-resistant resin. In addition, the preparation method of the polysiloxane containing a nitrogen heterocyclic structure provided by the present invention is simple and easy to implement industrially. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 The infrared spectra of nitrogen-containing heterocyclic polysiloxanes PS-11, PS-15, PS-14, and PS-18. DETAILED DESCRIPTION

[0046] Unless otherwise specified, the raw materials and catalysts in the following synthesis examples, embodiments and comparative examples of the present invention are purchased from commercial sources. Unless otherwise specified, the test methods of the present invention all adopt conventional methods, and the instrument settings all adopt the settings recommended by the manufacturer.

[0047] The abbreviations of ingredients used in this application are as follows:

[0048] MIBK: Methyl isobutyl ketone

[0049] ODPA: 4,4-oxydiphthalic anhydride

[0050]

[0051] ODA: 4,4'-diaminodiphenyl ether silane coupling agent monomer SCA:

[0052] SCA-1:

[0053]

[0054] SCA-2:

[0055]

[0056] SCA-3:

[0057]

[0058] SCA-4:

[0059]

[0060] SCA-5:

[0061]

[0062] SCA-6:

[0063]

[0064] SCA-7:

[0065]

[0066] SCA-8:

[0067] SCA-9:

[0068]

[0069] SCA-10:

[0070]

[0071] SCA-11:

[0072]

[0073] SCA-12:

[0074]

[0075] SCA-13:

[0076]

[0077] SCA-14:

[0078]

[0079] SCA-15:

[0080]

[0081] SCA-16:

[0082]

[0083] Among them, the nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 is prepared according to the method of Example 1 in Patent ZL202111145299.6, SCA-3 is prepared according to the method of Example 2 in Patent ZL202111145299.6, SCA-4 is prepared according to the method of Example 3 in Patent ZL202111145299.6, and SCA-5 is prepared according to the method of Example 4 in Patent ZL202111145299.6.

[0084] Preparation method of SCA-2: In a 500mL three-necked flask equipped with a stirrer and a thermometer, add 250.00g of solvent N-methylpyrrolidone and 0.1mol of 3,5-diamino-1,2,4-triazole in sequence, start stirring, and after 3,5-diamino-1,2,4-triazole is fully dissolved, slowly add 0.2mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride, and after the addition is completed, continue to react at 25°C for 20 hours, then add 0.4mol of N,N-dimethylformamide dimethyl acetal to the system, continue to react at 25°C for 4 hours, and after the reaction is completed, distill under reduced pressure to obtain SCA-2.

[0085] Preparation method of SCA-6:

[0086] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole were added in sequence, and stirring was started. After 2-(4-aminophenyl)-5-aminobenzimidazole was fully dissolved, 0.2 mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours. After the reaction was completed, the mixture was purified by vacuum distillation to obtain SCA-6.

[0087] Preparation method of SCA-7:

[0088] To a 500 mL three-necked flask equipped with a stirrer and a thermometer, 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole were added in sequence, and stirring was started. After 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole was fully dissolved, 0.2 mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours, and then 0.4 mol of pyridine was added to the reaction system. After stirring evenly, 0.4 mol of acetic anhydride was slowly added, and the reaction was carried out at 25° C. for 20 hours. After the reaction was completed, the solvent, acetic anhydride, and the generated acetic acid and pyridine in the system were removed by reduced pressure distillation to obtain SCA-7.

[0089] Preparation method of SCA-8: The same as SCA-6 except that 0.2 mol of 3-(trimethoxysilyl)propyl succinic anhydride was replaced by 0.2 mol of silane coupling agent SANAH (Shin-Etsu Chemical Co., Ltd.).

[0090] Preparation method of SCA-9: except replacing 0.2 mol of 3-(trimethoxysilyl)propyl succinic anhydride with 0.2 mol of silane coupling agent SANAH, the rest is the same as SCA-7.

[0091] The preparation method of SCA-10 is the same as that of SCA-6 except that 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole is replaced by 0.1 mol of 2-(4-aminophenyl)-5-aminobenzoxazole.

[0092] Preparation method of SCA-11: except that 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole is replaced by 0.1 mol of 2-(4-aminophenyl)-5-aminobenzoxazole, the rest is the same as SCA-7.

[0093] Preparation method of SCA-12: except that 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole is replaced by 0.1 mol of 2-(4-aminophenyl)-5-aminobenzoxazole, the rest is the same as SCA-8.

[0094] Preparation method of SCA-13: except replacing 0.1 mol of 2-(4-aminophenyl)-5-aminobenzimidazole with 0.1 mol of 2-(4-aminophenyl)-5-aminobenzoxazole, the rest is the same as SCA-9.

[0095] Preparation method of SCA-14: To a 500mL three-necked flask equipped with a stirrer and a thermometer, add 250.00g of solvent N-methylpyrrolidone and 0.1mol of 2-(4-aminophenyl)-5-aminobenzoxazole in sequence, start stirring, and after 2-(4-aminophenyl)-5-aminobenzoxazole is fully dissolved, slowly add 0.2mol of silane coupling agent SANAH, and after the addition is completed, continue to react at 25°C for 20 hours, then add 0.4mol of N,N-dimethylformamide diethyl acetal to the system, continue to react at 25°C for 4 hours, and after the reaction is completed, distill under reduced pressure to obtain SCA-14.

[0096] Preparation method of SCA-15: To a 500mL three-necked flask equipped with a stirrer and a thermometer, add 250.00g of solvent N-methylpyrrolidone and 0.1mol of 4,4'-diaminodiphenyl ether in sequence, start stirring, and after 4,4'-diaminodiphenyl ether is fully dissolved, slowly add 0.2mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride, and after the addition is completed, continue to react at 25°C for 20 hours. After the reaction is completed, distill under reduced pressure to obtain SCA-15.

[0097] Preparation method of SCA-16: Add 250.00 g of solvent N-methylpyrrolidone and 0.1 mol of 4,4'-diaminobenzanilide in sequence to a 500 mL three-necked flask equipped with a stirrer and a thermometer, start stirring, and after 4,4'-diaminobenzanilide is fully dissolved, slowly add 0.2 mol of silane coupling agent 3-(trimethoxysilyl)propyl succinic anhydride, and continue to react at 25° C. for 20 hours after the addition is completed. After the reaction is completed, distill under reduced pressure to obtain SCA-16.

[0098] The silane coupling agent was characterized by hydrogen nuclear magnetic resonance spectroscopy. Some hydrogen spectrum information is as follows:

[0099]

[0100]

[0101] Synthesis example 1

[0102] Under nitrogen protection, 100 g of methyl isobutyl ketone (MIBK), 30 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1, and 1.5 g of p-toluenesulfonic acid were added to a 250 ml three-necked flask, and the mixture was stirred and mixed evenly, and the system temperature was maintained at 10° C. (reaction temperature 1) to obtain a mixed solution; 150 g of deionized water was dropped into the mixed solution within 4 hours. After the addition was completed, the mixture was kept at 10° C. for 4 hours, and then the temperature was raised to 70° C. (reaction temperature 2) and the reaction was continued for 10 hours; after the reaction was completed, the organic layer was taken out, and the volatiles were evaporated off using a rotary evaporator to obtain nitrogen-containing heterocyclic polysiloxane PS-1.

[0103] Synthesis example 2-20

[0104] The nitrogen-containing heterocyclic polysiloxanes PS-2 to PS-20 were prepared by referring to the method of Synthesis Example 1. The reaction conditions used were selected according to Table 1 below.

[0105] Table 1

[0106]

[0107]

[0108] The synthesized polysiloxane samples were tested by the KBr tablet method using an infrared spectrometer (Shimadzu, IRAffinity-1S) to detect whether the polysiloxane of the present invention was successfully prepared. From the infrared characterization results, it can be seen that each polysiloxane has a wavelength of 1035-1160 cm -1 The Si-O-Si stretching vibration peak appears, indicating that the alkoxy group has been successfully converted into a Si-O-Si structure by hydrolysis. Among them, the infrared spectra of PS-11, PS-15, PS-14, and PS-18 are as follows: Figure 1 shown.

[0109] Comparative Synthesis Example 1

[0110] Polysiloxane PS-21 was prepared according to the method of Synthesis Example 1, except that 30 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 30 g of silane coupling agent monomer SCA-15.

[0111] Comparative Synthesis Example 2

[0112] Polysiloxane PS-22 was prepared according to the method of Synthesis Example 1, except that 30 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 30 g of silane coupling agent monomer SCA-16.

[0113] Preparation of resin composition

[0114] Example 1

[0115] Synthesis of polyimide precursor C-1:

[0116] 62.04 g (0.2 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was placed in a 1000 mL three-necked flask, 120.00 g of γ-butyrolactone (GBL) was added, and the mixture was stirred evenly. Then, 80.00 g of a GBL solution containing 39.06 g (0.19 mol) of 4,4'-diaminodiphenyl ether (ODA) was added within 60 min, and the mixture was reacted at 25 ° C for 12 h to obtain 300.1 g of a polyamic acid solution with a solid content of 33.35%.

[0117] The weight average molecular weight (M) of the resin was measured by gel permeation chromatography (standard polystyrene conversion). w The chromatograph used in the determination is LC-20AD produced by Shimadzu Corporation of Japan, the chromatographic column is KF-804 produced by Showa Denko, and the detector is RID-20A produced by Shimadzu Corporation of Japan. The molecular weight of the obtained polyamic acid is Mw: 28021.

[0118] 3.00 g of nitrogen-containing heterocyclic polysiloxane PS-1 obtained in Synthesis Example 1 was added to the polyamic acid solution and fully dissolved, and then filtered using a 1.0 μm filter membrane to obtain a resin composition. The viscosity was measured at 25° C. to be 3000 cP.

[0119] Examples and Comparative Examples

[0120] The resin composition was prepared by referring to the method of Example 1, except that the mass of the polyimide precursor C-1 and the structure and mass of the nitrogen-containing heterocyclic polysiloxane in each example and comparative example were selected according to Table 2 below.

[0121] Table 2

[0122]

[0123]

[0124] The effects of the nitrogen-containing heterocyclic polysiloxane and the resin composition prepared by the present invention were evaluated as follows:

[0125] 1. Adhesion peeling test between resin cured film and substrate

[0126] Each resin composition sample was evenly coated on a substrate (silicon wafer) using a coating machine, and then placed on a heating table at 120°C for 3 minutes for soft baking to obtain a resin film with a film thickness of 10 to 20 um. A grid was cut into 10 rows × 10 columns of squares using a grid cutter (BYK-Gardner A-5125), and then the film was placed in a vacuum oxygen-free oven (MOLZK-32D1) for heat treatment: heat treatment at 170°C for 30 minutes, then heated to 320°C after 1 hour, and treated at 320°C for 1 hour to finally obtain a cured film. Finally, a peeling test was performed using a tape (special transparent 3M tape) in accordance with the national standard GB / T 9286-1998 for the cross-cutting test of paint and varnish films, and the number of grids peeled off was recorded as the peeling condition before the PCT test.

[0127] A cured film was obtained by the same method as above, and placed in a PCT test box for a 200-hour PCT aging test (121°C, 2 atmospheres of saturated steam; PCT-30 of Dongguan Hongjin Technology). After the PCT test was completed, a peeling test was performed using tape using the same method as above, and the number of grids peeled off was recorded as the peeling condition after the PCT test.

[0128] In the adhesive peeling test, the number of peeled pieces was considered "best" when it was less than 5, "good" when it was less than 10, "slightly good" when it was less than 30, and "poor" when it was 30 or more.

[0129] 2. Glass transition temperature test

[0130] The cured film was obtained according to the method of the adhesive peeling test between the resin cured film and the substrate. About 10 g of the cured film obtained at 320°C was placed in an aluminum standard container and the glass transition temperature (Tg) was measured using a differential scanning calorimeter DSC-25 (TA Instruments Waters, USA). The film was first pre-dried at 80°C for 1 hour and then measured at a heating rate of 20°C / min.

[0131] 3. Tensile strength test

[0132] A cured film was obtained according to the method of the adhesion peeling test between the resin cured film and the substrate, and the cured film was cut into sample strips with a size of 40 mm in length and 5 mm in width. The tensile strength of the sample strips was tested using DMA-850 (TA Instruments Waters, USA) at a temperature of 150°C, a tensile force range of 0-18N, and a rate of 3N / min.

[0133] 4. Chemical resistance

[0134] Each resin composition sample was uniformly coated on a silicon wafer using a coating machine, and then placed on a heating table (HT-300 experimental electric heating plate, Guangzhou Gedan Instrument Co., Ltd.) at 120°C for 3 minutes for soft baking to obtain a resin film with a film thickness of 10 to 20 μm. The film was then placed in a vacuum oxygen-free oven (MOLZK-32D1) and heat-treated at 170°C for 30 minutes under nitrogen atmosphere protection, then heated to 320°C after 1 hour, and treated at 320°C for 1 hour, and then naturally cooled to below 50°C in the oven to finally obtain a cured film. The cured film was immersed in a 10wt% sodium hydroxide (NaOH) aqueous solution, a 10vol% sulfuric acid aqueous solution, and N-methylpyrrolidone (NMP) at 50°C for 30 minutes, respectively, to observe whether there were cracks.

[0135] 5. Experimental results

[0136] The resin composition prepared above was evaluated according to the method described above. The results are shown in Tables 3 and 4.

[0137] Table 3

[0138]

[0139]

[0140]

[0141] Table 4

[0142]

[0143]

[0144] From the above table we can see that:

[0145] It can be seen from the experimental results of Example 1, Examples 7 to 26, and Comparative Example 1 that the resin to which the nitrogen-containing heterocyclic polysiloxane compound of the present invention is added exhibits better chemical resistance, adhesion and other properties than the resin without the addition, and also has a higher glass transition temperature and tensile strength.

[0146] From the experimental results of Example 1, Examples 7 to 26, and Comparative Examples 2 to 3, it can be seen that the resin added with the nitrogen-containing heterocyclic polysiloxane compound of the present invention has a more obvious effect on improving chemical resistance, adhesion, glass transition temperature and tensile strength than the resin added with the polysiloxane compound without a nitrogen heterocyclic structure.

[0147] The nitrogen heterocycle of the polysiloxane of Examples 1 and 12 to 15 is a triazole group, and the nitrogen heterocycle of the polysiloxane of Examples 16 to 24 is an imidazolyl group or an oxazolyl group. From the experimental results, the glass transition temperature of Examples 16 to 24 is 9 to 16°C higher than that of Examples 1 and 12 to 15, and the overall tensile strength performance is also higher. Therefore, it can be seen that the polysiloxane containing imidazolyl or oxazolyl groups is better than the polysiloxane containing triazole groups.

[0148] From the comparison of Examples 1 to 6 and Comparative Example 1, it can be found that when the content of nitrogen-containing heterocyclic polysiloxane is 0.5%, the adhesion, chemical resistance, glass transition temperature and tensile strength improvement effects after PCT are poor, so the preferred ratio is 1% to 20%.

Claims

1. A nitrogen-containing heterocyclic polysiloxane, characterized in that: It has the structural formula shown in general formula (1): Wherein, Y is selected from at least one of the structures shown in formula (2) to formula (5), and * represents an insertion site: Wherein, R1 is selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms; Wherein, W is at least one of the structures ①, ②, and ③ in the following formula (6), and * represents an accession site: Here, R2 represents a hydrogen atom, and R3, R4, R5, and R6 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

2. The nitrogen-containing heterocyclic polysiloxane according to claim 1, characterized in that R1 is selected from hydrogen atom, methyl group, ethyl group, butyl group, hydroxyethyl group of methacrylate; R3, R4, R5, R6 are independently selected from hydrogen atom, methyl group, ethyl group.

3. A method for preparing the nitrogen-containing heterocyclic polysiloxane as claimed in claim 1, characterized in that The following steps are involved: Step 1, under gas protection, stirring and mixing the organic solvent, nitrogen-containing heterocyclic silane coupling agent monomer and catalyst; Step 2, controlling the temperature of the mixture in step 1 at 0-40°C, adding water dropwise thereto, keeping the mixture warm for reaction after the addition is complete, and then raising the temperature to 50-100°C to continue the reaction; Step 3: After the reaction, the organic layer is separated and the volatiles are removed by distillation to obtain a nitrogen-containing heterocyclic polysiloxane.

4. The preparation method according to claim 3, characterized in that: The nitrogen-containing heterocyclic silane coupling agent monomer is selected from at least one of the structures shown in the following formula (7): Wherein, the definitions of R1 and W are consistent with those in claim 1, and R7 is a hydrocarbon group having 1 to 10 carbon atoms.

5. The preparation method according to claim 3, characterized in that: The method comprises at least one of the following reaction conditions: a. In step 1, the organic solvent is selected from at least one of hydrocarbons, ketones, esters, ethers and alcohols; b. In step 1, the catalyst is one of an acid, an alkali metal compound or an organic base; c. In step 1, the mass ratio of nitrogen-containing heterocyclic silane coupling agent monomer, organic solvent, and catalyst is 1: 0.5 to 20: 0.01 to 0.3; d. In step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:1 to 50; e. In step 2, the water addition time is 0.5 to 5 h; f. In step 2, the reaction is carried out at 0-40°C for 3-6 hours and at 50-100°C for 6-12 hours.

6. Use of the nitrogen-containing heterocyclic polysiloxane according to claim 1 or 2 as a heat-resistant resin modifier.

7. The use according to claim 6, characterized in that: The amount of the nitrogen-containing heterocyclic polysiloxane used is 0.1 to 20% of the mass of the heat-resistant resin.

8. The use according to claim 7, characterized in that: The amount of the nitrogen-containing heterocyclic polysiloxane used is 1 to 10% of the mass of the heat-resistant resin.

9. The use according to claim 6, characterized in that: The heat-resistant resin includes at least one of a polyimide resin, a polyimide precursor, a polybenzoxazole resin, a polybenzoxazole precursor, a polyamide resin, a polyamideimide resin, a polybenzimidazole resin, and a polybenzothiazole resin.

10. The use according to claim 9, characterized in that: The polyimide precursor is selected from polyamic acid or polyamic acid ester, and the polybenzoxazole precursor is selected from polyhydroxyamide.

Images