A polysiloxane, its preparation method and application

Abstract

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

Description

Technical Field

[0001] The invention relates to a polysiloxane and a preparation method and application thereof, in particular 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 polysiloxane, the polysiloxane having the structure can significantly enhance the thermal stability, mechanical properties and chemical resistance of the cured film of the 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 a first aspect of the present application, a polysiloxane with a special structure is provided.

[0006] A polysiloxane having the structural formula shown in the following general formula (1):

[0007]

[0008] 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 accession site:

[0009]

[0010] Furthermore, in the above formulas (2) to (5), R 1is 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, R 1 Selected from hydrogen atom, methyl, ethyl, butyl, methacrylate hydroxyethyl.

[0011] Furthermore, in the above formulae (2) to (5), W is selected from a nitrogen-containing heterocyclic structure, such as triazolyl, tetrazolyl, imidazole, oxazole, and the like.

[0012] Preferably, W is at least one of the structures shown in the following formula (6), and * represents an insertion site:

[0013]

[0014] Among them, in formula (6), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 At least one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, and an ester group is independently selected. 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, decyl, or a cycloalkyl group such as cyclopentyl or cyclohexyl, an aromatic group such as phenyl or tolyl, an aralkyl group such as benzyl, phenethyl, or phenylpropyl, or an unsaturated alkenyl group such as vinyl, allyl, butenyl, propenyl, isopropenyl, or phenylalkenyl.

[0015] Preferably, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are independently selected from a hydrogen atom, a saturated alkyl group having 1 to 3 carbon atoms, a carboxyl group having 1 to 5 carbon atoms, and an ester group. 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8are independently selected from a hydrogen atom, a saturated alkyl group having 1 to 3 carbon atoms, and a carboxyl group having 1 to 5 carbon atoms. More preferably, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 Each is independently selected from a hydrogen atom, a methyl group, an ethyl group, and a carboxyl group.

[0016] According to the second aspect of the present application, the present invention provides a method for preparing the above-mentioned polysiloxane. The method comprises the following steps:

[0017] Step 1: Under gas protection, the organic solvent, nitrogen-containing heterocyclic silane coupling agent monomer and catalyst are stirred and mixed uniformly;

[0018] Step 2: Control the temperature of the mixture in step 1 at 0-40°C, add water dropwise thereto, keep the mixture warm for reaction after the addition is complete, and then raise the temperature to 50-100°C to continue the reaction;

[0019] Step 3: After the reaction, the organic layer is separated and the volatile matter is removed by distillation to obtain polysiloxane.

[0020] 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):

[0021]

[0022] In formula (7), R 1 The definition of W is consistent with the above definition.

[0023] In formula (7), R 10 is selected from hydrocarbon groups having 1 to 10 carbon atoms. The hydrocarbon groups having 1 to 10 carbon atoms may be alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., cycloalkyl groups such as cyclopentyl and cyclohexyl, aromatic groups such as phenyl and tolyl, aralkyl groups such as benzyl, phenethyl, phenylpropyl, etc., and unsaturated alkenyl groups such as vinyl, allyl, butenyl, propenyl, isopropenyl, and phenylalkenyl. Preferably, R 10 is a saturated alkyl group having 1 to 10 carbon atoms, more preferably, R 10 It is methyl or ethyl.

[0024] Furthermore, 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 nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount equal to one times the nitrogen-containing heterocyclic monoamine H is slowly added. 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 amide 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 nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount of one times the nitrogen-containing heterocyclic monoamine H is slowly added. 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 nitrogen-containing heterocyclic monoamine H is mixed with a solvent, and then a silane coupling agent SANAH or 3-(trimethoxysilyl)propyl succinic anhydride in a molar amount of one times the nitrogen-containing heterocyclic monoamine H is slowly added. 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, reduced pressure distillation is performed to obtain an amide ester type nitrogen-containing heterocyclic silane coupling agent monomer.

[0031] Wherein, the nitrogen-containing heterocyclic monoamine H is selected from at least one of the structures shown in the following formula (8):

[0032]

[0033] In the above formula (8), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 The definition is consistent with the above definition.

[0034] Optionally, in step 1, the organic solvent is at least one of hydrocarbons, ketones, esters, ethers, alcohols, etc. The hydrocarbons include, for example, toluene, xylene, etc.; 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.

[0035] 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.

[0036] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the organic solvent is 1:0.25-10, for example, 1:0.25, 1:0.5, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, preferably 1:1-5.

[0037] Optionally, in step 1, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to the catalyst is 1:0.001-0.1, for example, 1:0.001, 1:0.002, 1:0.003, 1:0.004, 1:0.005, 1:0.006, 1:0.007, 1:0.008, 1:0.009, 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, preferably 1:0.005-0.05.

[0038] Optionally, in step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:0.5-25, 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, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, preferably 1:1-10.

[0039] 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.

[0040] 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.

[0041] According to the third aspect of the present application, the present invention provides the use of the above-mentioned polysiloxane as a heat-resistant resin modifier. The polysiloxane provided by the present invention can be used as a heat-resistant resin modifier to enhance the adhesion between the heat-resistant resin and the substrate. It can also be used to enhance the thermal stability, mechanical properties, and chemical resistance of the heat-resistant resin.

[0042] 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.

[0043] Optionally, the polyimide precursor is selected from polyamic acid or polyamic acid ester.

[0044] Optionally, the polybenzoxazole precursor is selected from polyhydroxyamides.

[0045] Optionally, the amount of the polysiloxane is 0.1-20% 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 1-20%.

[0046] Optionally, the polysiloxane may be one, or two or more. The polysiloxane provided by the present invention has a special structure and a nitrogen-containing heterocyclic ring. The polysiloxane can be used as a heat-resistant resin modifier, which 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 provided by the present invention is simple and easy to implement industrially. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 These are the infrared spectra of polysiloxanes PS-11, PS-17, PS-19, and PS-20. DETAILED DESCRIPTION

[0048] Unless otherwise specified, the raw materials and catalysts in the synthesis examples, embodiments and comparative examples of the present invention are purchased from commercial sources. Unless otherwise specified, the testing methods are conventional methods, and the instrument settings are the settings recommended by the manufacturer.

[0049] The abbreviations of the ingredients used in this application are as follows: MIBK: methyl isobutyl ketone

[0050] ODPA: 4,4-oxydiphthalic anhydride

[0051]

[0052] ODA: 4,4'-diaminodiphenyl ether silane coupling agent monomer SCA:

[0053]

[0054]

[0055]

[0056]

[0057] Preparation of silane coupling agent SCA-1~SCA-19:

[0058] Preparation of SCA-1:

[0059] 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 4-aminotriazole were added in sequence, and stirring was started. After 4-aminotriazole was fully dissolved, 0.1 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 reaction was purified by vacuum distillation to obtain SCA-1.

[0060] Preparation of SCA-2:

[0061] 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 4-aminotriazole were added in sequence, and stirring was started. After 4-aminotriazole was fully dissolved, 0.1 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. Then, 0.2 mol of pyridine was added to the reaction system. After stirring evenly, 0.2 mol of acetic anhydride was slowly added. 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-2.

[0062] Preparation of SCA-3:

[0063] The same as SCA-1 except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride was replaced by 0.1 mol of silane coupling agent SANAH (Shin-Etsu Chemical Co., Ltd.).

[0064] Preparation of SCA-4:

[0065] The preparation method is the same as SCA-2 except that 0.1 mol of 3-(trimethoxysilyl)propyl succinic anhydride is replaced by 0.1 mol of silane coupling agent SANAH.

[0066] Preparation of SCA-5:

[0067] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 3-amino-1,2,4-triazole.

[0068] Preparation of SCA-6:

[0069] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-amino-1H-1,2,4-triazole-3-carboxylic acid.

[0070] Preparation of SCA-7:

[0071] The preparation method is the same as SCA-1 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0072] Preparation of SCA-8:

[0073] The preparation method is the same as SCA-2 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0074] Preparation of SCA-9:

[0075] The preparation method is the same as SCA-3 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 5-aminotetrazolyl.

[0076] Preparation of SCA-10:

[0077] The same as SCA-4 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 5-aminotetrazolyl.

[0078] Preparation of SCA-11:

[0079] The same method as SCA-1 was used except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 1-methyl-5-aminotetrazolyl.

[0080] Preparation of SCA-12:

[0081] The reaction was the same as SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminoimidazole.

[0082] Preparation of SCA-13:

[0083] The preparation method is the same as SCA-3 except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of 2-aminoimidazole.

[0084] Preparation of SCA-14:

[0085] The reaction was the same as SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminooxazole.

[0086] Preparation of SCA-15:

[0087] The reaction was the same as SCA-3 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 2-aminooxazole.

[0088] Preparation of SCA-16:

[0089] 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-aminoimidazole were added in sequence, and stirring was started. After the 2-aminoimidazole was fully dissolved, 0.1 mol of silane coupling agent SANAH was slowly added. After the addition was completed, the reaction was continued at 25° C. for 20 hours, and then 0.2 mol of N,N-dimethylformamide dimethyl acetal was added to the system, and the reaction was continued at 25° C. for 4 hours. After the reaction was completed, it was distilled under reduced pressure to obtain SCA-16.

[0090] Preparation of SCA-17:

[0091] The same as SCA-16 except that 0.1 mol 2-aminoimidazole was replaced by 0.1 mol 2-aminooxazole.

[0092] Preparation of SCA-18:

[0093] The reaction mixture was the same as that of SCA-1 except that 0.1 mol of 4-aminotriazole was replaced by 0.1 mol of 3-aminophenol.

[0094] Preparation of SCA-19:

[0095] Except that 0.1 mol of 4-aminotriazole is replaced by 0.1 mol of p-aminobenzoic acid, the rest is the same as SCA-1. The silane coupling agent is characterized by hydrogen nuclear magnetic resonance spectrum, and some hydrogen spectrum information is as follows:

[0096]

[0097] Synthesis example 1

[0098] Under nitrogen protection, 100 g of methyl isobutyl ketone (MIBK), 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1, and 0.5 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 above 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 polysiloxane PS-1.

[0099] Synthesis example 2-23

[0100] The synthesis of polysiloxanes PS-2 to PS-23 was carried out by referring to the steps of Synthesis Example 1, except that the reaction conditions used were selected according to Table 1 below.

[0101] Table 1

[0102]

[0103]

[0104] 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 -1The 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-17, PS-19, and PS-20 are as follows: Figure 1 shown.

[0105] Comparative Synthesis Example 1

[0106] Polysiloxane PS-24 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-18.

[0107] Comparative Synthesis Example 2

[0108] Polysiloxane PS-25 was prepared according to the method of Synthesis Example 1, except that 20 g of nitrogen-containing heterocyclic silane coupling agent monomer SCA-1 was replaced with 20 g of silane coupling agent monomer SCA-19.

[0109] Preparation of resin composition

[0110] Example 1

[0111] Synthesis of polyimide precursor C-1:

[0112] 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 (0.095 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%.

[0113] 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.

[0114] 3.00 g of the 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 to 3400 cP.

[0115] Examples and Comparative Examples

[0116] 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 polysiloxane in each example and comparative example were selected according to Table 2 below.

[0117] Table 2

[0118]

[0119]

[0120] The effects of the polysiloxane and the resin composition prepared by the present invention were evaluated as follows:

[0121] 1. Adhesion peeling test between resin cured film and substrate

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 2. Glass transition temperature test

[0126] 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.

[0127] 3. Tensile strength test

[0128] 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.

[0129] 4. Chemical resistance

[0130] 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.

[0131] 5. Experimental results

[0132] The resin composition prepared above was evaluated according to the method described above. The results are shown in Tables 3 and 4.

[0133] Table 3

[0134]

[0135]

[0136] Table 4

[0137]

[0138]

[0139] From the above table we can see that:

[0140] It can be seen from the experimental results of Example 1, Examples 7 to 29, 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.

[0141] It can be seen from the experimental results of Example 1, Examples 7 to 29, and Comparative Examples 2 to 3 that the resin to which the nitrogen-containing heterocyclic polysiloxane compound of the present invention is added has a more obvious effect on improving chemical resistance, adhesion, glass transition temperature and tensile strength than the resin to which the polysiloxane compound without a nitrogen heterocyclic structure is added.

[0142] From the experimental results of Example 1 and Examples 7 to 29, when the nitrogen heterocyclic ring is imidazole or oxazole, the effect of improving the tensile strength and glass transition temperature is better than that of other nitrogen heterocyclic siloxanes such as triazole and tetrazolyl.

[0143] 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 polysiloxane, characterized in that: It has the structural formula shown in general formula (1): (1) Wherein, Y is selected from at least one of the structures shown in formula (2) to formula (5), and * represents an insertion site: (2)； (3)； (4)； (5)； 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 shown in the following formula (6), and * represents an accession site: （6） Here, R2, R6, R8, and R9 each independently represent at least one of a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, and an ester group.

2. The polysiloxane according to claim 1, characterized in that R1 is selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, a butyl group, and a hydroxyethyl group of methacrylate; R2, R6, R8, and R9 independently represent a hydrogen atom, a methyl group, an ethyl group, and a carboxyl group.

3. A method for preparing the polysiloxane according to claim 1, characterized in that The following steps are involved: Step 1: Under gas protection, the organic solvent, nitrogen-containing heterocyclic silane coupling agent monomer and catalyst are stirred and mixed uniformly; Step 2: Control the temperature of the mixture in step 1 at 0-40°C, add water dropwise thereto, keep the mixture warm for reaction after the addition is complete, and then raise the temperature to 50-100°C to continue the reaction; Step 3: After the reaction, the organic layer is separated and the volatile matter is removed by distillation to obtain 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): （7） Wherein, the definitions of R1 and W are consistent with those in claim 1, R 10 It 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: 0.25-10: 0.001-0.1; d. In step 2, the mass ratio of the nitrogen-containing heterocyclic silane coupling agent monomer to water is 1:0.5 to 25; 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 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 polysiloxane used is 0.1-20% of the mass of the heat-resistant resin.

8. The use according to claim 6, characterized in that: The amount of polysiloxane used is 1 to 20% 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.

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