Synthesis method for and use of environmentally-friendly solvent-free methylphenyl silicone resin

Abstract

Disclosed in the present invention are a synthesis method for and a use of an environmentally friendly solvent-free methylphenyl silicone resin. The methylphenyl silicone resin prepared by the present invention is applied to a paint film and has relatively good heat resistance, and after being roasted for 2 hours at 500ºC, the surface of the paint film remains intact without peeling or flaking; grade 1 adhesion is achieved, and the impact strength reaches 52 kg·cm; and the resin has relatively good film forming performance. In the present invention, a butyltin and a carboxylate copper complex are introduced; these resin catalysts show higher catalytic activity, especially in promoting the hydrolysis of a silane compound, thus improving the synthesis efficiency of the product methylphenyl silicone resin; the introduction of a crown ether structure can contribute to the control of a reaction pathway, and the occurrence of side reactions can be reduced due to a complexing effect of the crown ether structure, thereby improving the selectivity of the product; and the macroporous structure achieves easy regeneration and reusability, thereby facilitating industrial application.

Description

Synthesis method and application of environment-friendly solvent-free methyl phenyl silicone resin TECHNICAL FIELD

[0001] The present application relates to the field of environmental protection, and particularly relates to a synthesis method and application of environment-friendly solvent-free methyl phenyl silicone resin. BACKGROUND

[0002] Methyl phenyl silicone resin is widely used in aerospace, mechanical electronics, building and other fields due to its excellent high and low temperature resistance, radiation resistance and electrical insulation performance. One of the largest uses of the material is to prepare silicone coatings, especially special coatings to meet the special requirements of the military industry.

[0003] Chinese patent CN108707231A: A preparation method of methyl phenyl silicone resin and coating is provided. All or part of methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and diphenyldichlorosilane are combined as monomer raw materials, and hydrolysis is carried out in the presence of water-insoluble organic solvent to generate organosiloxane alcohol. A nucleophilic reaction catalyst 8% tetramethylammonium hydroxide butanol solution is added for catalytic condensation. Finally, a high-reactivity organosilicon resin polymer with a specific structure is obtained. 20g of the prepared methyl phenyl silicone resin is weighed, a curing agent butyl titanate is added, and uniform stirring is carried out for 1h. The methyl phenyl silicone resin coating is uniformly coated on an iron material substrate, and is cured at room temperature for 2-3 days to successfully construct the methyl phenyl silicone resin coating.

[0004] Chinese patent CN105111440B: A continuous and environment-friendly preparation process of methyl phenyl silicone resin for high-temperature resistant coating is disclosed. The technical scheme is as follows: phenyltrichlorosilane, diphenyldichlorosilane, methyltrichlorosilane and dimethyldichlorosilane are mixed in a mass ratio of 1-20:1-10:1-10:1-20. The mass of benzene solvent is 1-3 times the mass of the mixed chlorosilane monomers. The mixture is then introduced into a tubular hydrolysis reactor to react with dilute acid water. The mass of the dilute acid water is 2-5 times the mass of the mixed chlorosilane monomers. The hydrolyzate is washed with water in stages to neutralization. The mixture is continuously concentrated under vacuum. When the volume of the mixture in the condensation and polycondensation kettle reaches 50%-60% of the volume of the kettle, polycondensation reaction is carried out. After the polycondensation is completed, the mixture is detected, filtered and packaged. The solvent is recycled.

[0005] Chinese patent CN117285711A: A preparation method of high-yield methyl phenyl silicone resin is disclosed, which relates to the technical field of chemical synthesis of methyl phenyl silicone resin. The method uses methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane and diphenyldichlorosilane as silane monomer raw materials, and dimethylbenzene and water as solvents for hydrolysis reaction and polycondensation reaction. The methyl phenyl silicone resin is prepared by controlling the reaction temperature and reaction time of the hydrolysis.

[0006] The above patent and prior art use organic chlorosilane to hydrolyze in the presence of toluene, xylene and other solvents, then separate the acid water, and wash the resin liquid to neutral. This method will produce a large amount of low-concentration acid water, use organic solvents, and cause environmental pollution. In addition, the obtained silicone resin needs to be stored in a solvent, so there are safety problems in storage and transportation. SUMMARY

[0007] The application aims to provide a synthesis method and application of an environmentally friendly solvent-free methylphenyl silicone resin to solve the problems involved in the background art.

[0008] Technical scheme: A synthesis method and application of an environmentally friendly solvent-free methylphenyl silicone resin, the operation steps of which are as follows:

[0009] S1: Take 100-200 parts of phenyltrimethoxysilane, 750-850 parts of dimethyl carbonate, 80-100 parts of octaphenylcyclotetrasiloxane, and 30-50 parts of a catalyst by weight, and add them to a reaction kettle, then stir and heat to react, and then filter off the catalyst;

[0010] S2: Heat to 160-180°C and remove low molecular weight substances under vacuum, then hydrolyze the obtained product with 300-400 parts of phenyltrimethoxysilane, 80-100 parts of methyltrimethoxysilane, and 50-60 parts of high-purity water, remove the byproduct methanol after hydrolysis, and obtain a methylphenyl silicone resin.

[0011] As a preferred scheme, the reaction temperature of S1 is 80-100°C, and the time is 4-8h.

[0012] As a preferred scheme, the hydrolysis temperature of S2 is 60-70°C, and the time is 4-6h.

[0013] As a preferred scheme, the application of the methylphenyl silicone resin is as follows:

[0014] Dissolve 10-20 parts of methylphenyl silicone resin in 60-80 parts of dimethyl carbonate, filter, and then brush it on a steel plate, dry and cure to obtain a resin paint film.

[0015] As a preferred scheme, the thickness of the coating film is 40-60μm.

[0016] As a preferred scheme, the curing temperature is 180-200°C, and the time is 60-120min.

[0017] As a preferred scheme, the preparation method of the catalyst is as follows:

[0018] A1: Perform plasma treatment on a macroporous cationic styrene resin with 3-mercaptopropionic acid vapor to obtain a mercapto macroporous cationic styrene resin;

[0019] A2: ultrasonic dispersion of 100-200 parts of mercapto macroporous cationic styrene resin in 1000-1400 parts of ethanol containing 0.2-0.5 parts of methyl allyl tri-n-butyl tin, 3-7 parts of (Z)-9-octadecenoic acid copper (II) salt, 0.005-0.03 parts of 4-vinylbenzo-18-crown-6, adding 0.5-2wt% of the mass percentage of the mercapto macroporous cationic styrene resin to the photoinitiator, irradiating under 230nm-400nm ultraviolet lamp for 30-100min, filtering, washing the product with ethanol, and drying to obtain the catalyst.

[0020] As a preferred solution, the photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone or dimethylbenzene.

[0021] As a preferred solution, the processing time of the plasma treatment device is 30s-90s, the gas flow of 3-mercaptopropionic acid vapor is 10-30sccm, the processing frequency is 10-15MHz, and the power is 70-80W.

[0022] As a preferred solution, the macroporous cationic styrene resin is selected from D001 or Or macroporous cationic styrene resin.

[0023] Reaction mechanism: the mercapto macroporous cationic styrene resin reacts with methyl allyl tri-n-butyl tin, (Z)-9-octadecenoic acid copper (II) salt, and 4-vinylbenzo-18-crown-6 through thiol-ene click chemistry to obtain a cationic styrene resin containing butyl tin, carboxyl copper complex, crown ether, and sulfonic acid group; as a catalyst for the hydrolysis synthesis of methyl phenyl silicone resin from phenyl trimethoxysilane, the carboxyl copper complex part in the introduced (Z)-9-octadecenoic acid copper (II) salt can provide Lewis acid sites that can activate water molecules for nucleophilic attack, thereby promoting the hydrolysis of silane compounds; the introduced crown ether structure can act as a phase transfer catalyst by complexing metal ions to improve their solubility in the organic phase, thereby accelerating the chemical reaction between the interfaces.

[0024] Beneficial effects: the present application is an environmentally friendly solvent-free synthesis method and application of methyl phenyl silicone resin, which has the following remarkable effects compared with the prior art:

[0025] 1. The present application does not use toluene, xylene and other solvents to prepare methyl phenyl silicone resin, and there is no environmental pollution, which is a green and environmentally friendly process;

[0026] 2、The methyl phenyl silicone resin prepared by the method has good heat resistance, and after being baked at 500 DEG C for 2h, the paint film surface is intact, does not peel and does not fall off.

[0027] 3、The methyl phenyl silicone resin prepared by the method has good film forming performance, and the adhesion reaches level 1 and the impact strength reaches 52 kg.cm.

[0028] 4、The resin catalyst shows higher catalytic activity due to the introduction of the butyl tin and carboxyl copper complex, especially in promoting the hydrolysis of silane compounds, thereby improving the synthesis efficiency of the product methyl phenyl silicone resin; the introduction of the crown ether structure may help to control the reaction path, and may reduce the occurrence of side reactions through complexation, thereby increasing the selectivity of the product; and due to the large pore structure, it is easy to regenerate and reuse, which is conducive to the realization of industrial application. DETAILED DESCRIPTION

[0029] In the following description, a large number of specific details are given to provide a more thorough understanding of the present application. However, it is apparent to those skilled in the art that the present application can be implemented without one or more of these details. In other cases, some technical features known to those skilled in the art are not described in order not to obscure the present application.

[0030] Example 1

[0031] A synthesis method and application of an environmentally friendly solvent-free methyl phenyl silicone resin, the operation steps of which are as follows:

[0032] S1: 100g of phenyl trimethoxysilane, 750g of dimethyl carbonate, 80g of octaphenylcyclotetrasiloxane and 30g of catalyst are weighed and added to a reaction kettle, then stirring is started and the reaction is carried out after temperature rising, and then the catalyst is filtered off;

[0033] S2: the temperature is raised to 160 DEG C and low molecular weight is removed under vacuum, and then the obtained product is hydrolyzed with 300g of phenyl trimethoxysilane, 80g of methyl trimethoxysilane and 50g of high-purity water, and then the by-product methanol is removed after hydrolysis to obtain a methyl phenyl silicone resin.

[0034] The reaction temperature of S1 is 80 DEG C, and the time is 4h.

[0035] The hydrolysis temperature of S2 is 60 DEG C, and the time is 4h.

[0036] The application of the methyl phenyl silicone resin is as follows:

[0037] 10g of methyl phenyl silicone resin is dissolved in 60g of dimethyl carbonate, filtered, and then coated on a steel plate, and after drying and curing, a resin paint film is obtained.

[0038] The coating film thickness is 40 μm.

[0039] The curing temperature is 180℃, and the time is 60 min.

[0040] The preparation method of the catalyst is:

[0041] A1: The macroporous cationic styrene resin is subjected to plasma treatment with 3-mercaptopropionic acid vapor to obtain a mercapto macroporous cationic styrene resin;

[0042] A2: 100 g of the mercapto macroporous cationic styrene resin is ultrasonically dispersed in 1000 g of ethanol containing 0.2 g of methyl allyl tri-n-butyl tin, 3 g of (Z)-9-octadecenoic acid copper (II) salt, and 0.005 g of 4-vinylbenzo-18-crown-6, 0.5 wt% of a photoinitiator based on the mass of the mercapto macroporous cationic styrene resin is added, and irradiation is performed under a 230 nm ultraviolet lamp for 30 min. The product is filtered, washed with ethanol, and dried to obtain the catalyst.

[0043] The photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0044] The treatment time of the plasma treatment device is 30 s, the gas flow of the 3-mercaptopropionic acid vapor is 10 sccm, the treatment frequency is 10 MHz, and the power is 70 W.

[0045] The macroporous cationic styrene resin is selected from D001 macroporous cationic styrene resin.

[0046] Example 2

[0047] A method for synthesizing an environmentally friendly solvent-free methyl phenyl silicone resin and its application, the operation steps are:

[0048] S1: 140 g of phenyl trimethoxysilane, 780 g of dimethyl carbonate, 85 g of octaphenylcyclotetrasiloxane, and 35 g of a catalyst are weighed and added to a reaction kettle, stirring is started, and after warming and reaction, the catalyst is filtered off;

[0049] S2: The temperature is raised to 165℃, and low molecular weight is removed under vacuum. The obtained product is hydrolyzed with 340 g of phenyl trimethoxysilane, 85 g of methyl trimethoxysilane, and 54 g of high-purity water. After hydrolysis, the byproduct methanol is removed to obtain a methyl phenyl silicone resin.

[0050] The reaction temperature of S1 is 85℃, and the time is 5 h.

[0051] The hydrolysis temperature of S2 is 65℃, and the time is 5 h.

[0052] The application of the methyl phenyl silicone resin is:

[0053] 14g of the methyl phenyl silicone resin is dissolved in 65g of dimethyl carbonate, filtered, and then applied to a steel plate, dried, and cured to obtain a resin paint film.

[0054] The thickness of the paint film is 45μm.

[0055] The curing temperature is 185℃, and the time is 80min.

[0056] The preparation method of the catalyst is:

[0057] A1: macroporous cationic styrene resin is subjected to plasma treatment with 3-mercaptopropionic acid vapor to obtain mercapto macroporous cationic styrene resin;

[0058] A2: 140g of the mercapto macroporous cationic styrene resin is ultrasonically dispersed in 1100g of ethanol containing 0.3g of methyl allyl tri-n-butyl tin, 4g of (Z)-9-octadecenoic acid copper (II) salt, and 0.01g of 4-vinylbenzo-18-crown-6, 1wt% of a photoinitiator based on the mass of the mercapto macroporous cationic styrene resin is added, and irradiation is performed under a 300nm ultraviolet lamp for 50min, the product is filtered, washed with ethanol, and dried to obtain the catalyst.

[0059] The photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0060] The treatment time of the plasma treatment device is 50s, the gas flow of the 3-mercaptopropionic acid vapor is 15sccm, the treatment frequency is 12MHz, and the power is 75W.

[0061] The macroporous cationic styrene resin is selected from macroporous cationic styrene resin.

[0062] Example 3

[0063] A synthesis method and application of an environmentally friendly solvent-free methyl phenyl silicone resin, the operation steps of which are:

[0064] S1: 180g of phenyl trimethoxysilane, 830g of dimethyl carbonate, 95g of octaphenylcyclotetrasiloxane, and 45g of a catalyst are weighed into a reaction kettle, stirring is started, and after warming and reaction, the catalyst is filtered off;

[0065] S2: the temperature is raised to 175℃, low molecular weight is removed under vacuum, and the obtained product is hydrolyzed with 380g of phenyl trimethoxysilane, 95g of methyl trimethoxysilane, and 58g of high-purity water, and after hydrolysis, the byproduct methanol is removed to obtain a methyl phenyl silicone resin.

[0066] The reaction temperature of S1 is 95℃, and the time is 7h.

[0067] The hydrolysis temperature of S2 is 65℃, and the time is 5h.

[0068] The application of the methyl phenyl silicone resin is:

[0069] 18g of methyl phenyl silicone resin is dissolved in 75g of dimethyl carbonate, filtered, and then brushed on a steel plate. After drying and curing, a resin paint film is obtained.

[0070] The coating film thickness is 55μm.

[0071] The curing temperature is 195℃, and the time is 100min.

[0072] The preparation method of the catalyst is:

[0073] A1: A macroporous cationic styrene resin is subjected to plasma treatment with 3-mercaptopropionic acid vapor to obtain a mercapto macroporous cationic styrene resin;

[0074] A2: 180g of the mercapto macroporous cationic styrene resin is ultrasonically dispersed in 1300g of ethanol containing 0.4g of methyl allyl tri-n-butyl tin, 6g of (Z)-9-octadecenoic acid copper (II) salt, and 0.02g of 4-vinylbenzo-18-crown-6. A light initiator is added in an amount of 1.5wt% based on the mass of the mercapto macroporous cationic styrene resin. The mixture is irradiated under a 350nm ultraviolet lamp for 80min. The product is filtered, washed with ethanol, and dried to obtain the catalyst.

[0075] The light initiator is benzo pinacol.

[0076] The processing time of the plasma treatment device is 70s, the gas flow of 3-mercaptopropionic acid vapor is 25sccm, the processing frequency is 14MHz, and the power is 75W.

[0077] The macroporous cationic styrene resin is selected from A macroporous cationic styrene resin.

[0078] Example 4

[0079] A synthesis method and application of an environmentally friendly solvent-free methyl phenyl silicone resin, the operation steps of which are:

[0080] S1: 200g of phenyl trimethoxysilane, 850g of dimethyl carbonate, 100g of octaphenylcyclotetrasiloxane, and 50g of a catalyst are weighed into a reaction kettle, stirring is started, and then the reaction is carried out after heating. The catalyst is filtered out after the reaction.

[0081] S2: warming to 180℃, removing low molecular weight under vacuum, the obtained product and 400g phenyltrimethoxysilane, 100g methyltrimethoxysilane, 60g high purity water, hydrolysis, removing byproduct methanol after hydrolysis, obtaining methylphenylsilicone resin.

[0082] The reaction temperature of S1 is 100℃, and the reaction time is 8h.

[0083] The hydrolysis temperature of S2 is 70℃, and the reaction time is 6h.

[0084] The application of the methylphenylsilicone resin is:

[0085] 20g methylphenylsilicone resin is dissolved in 80g dimethyl carbonate, after filtration, the solution is coated on a steel plate, and after drying and curing, a resin paint film is obtained.

[0086] The thickness of the paint film is 60μm.

[0087] The curing temperature is 200℃, and the curing time is 120min.

[0088] The preparation method of the catalyst is:

[0089] A1: macroporous cationic styrene resin is treated by plasma with 3-mercaptopropionic acid vapor to obtain mercapto macroporous cationic styrene resin;

[0090] A2: 200g mercapto macroporous cationic styrene resin is ultrasonically dispersed in 1400g ethanol containing 0.5g methylallyl tri-n-butyl tin, 7g (Z)-9-octadecenoic acid copper (II) salt, and 0.03g 4-vinylbenzo-18-crown-6, 2wt% photoinitiator based on the mass of the mercapto macroporous cationic styrene resin is added, and the mixture is irradiated under a 400nm ultraviolet lamp for 100min, then the product is filtered, washed with ethanol, and dried to obtain the catalyst.

[0091] The photoinitiator is benzo pinacol.

[0092] The treatment time of the plasma treatment device is 90s, the gas flow of 3-mercaptopropionic acid vapor is 30sccm, the treatment frequency is 15MHz, and the power is 80W.

[0093] The macroporous cationic styrene resin is selected from macroporous cationic styrene resin.

[0094] Comparative Example 1

[0095] Except that methylallyl tri-n-butyl tin is not added, other conditions are the same as in Example 1.

[0096] Comparative Example 2

[0097] Example 1 except that (Z)-9-octadecenoic acid copper (II) salt was not added.

[0098] Comparative Example 3

[0099] Example 1 except that 4-vinylbenzo-18-crown-6 ether-6 was not added.

[0100] Example Resin Test Method:

[0101] 1. Heat resistance: determined according to GB / T 1735-1979; the resin paint film was placed in a muffle furnace, baked at 500°C for 2h, then removed, cooled to room temperature, and the surface condition of the coating film was observed.

[0102] 2. Impact resistance: determined according to GB / T 1732-1993.

[0103] 3. Adhesion test: determined according to GB / T 1720-1979.

[0104] Example Test Results:

[0105] From the data analysis of the above examples and comparative examples, the methylphenyl silicone resin prepared in the present application has good heat resistance, the paint film surface is intact, does not peel and does not fall off after baking at 500°C for 2h; the adhesion reaches level 1, the impact strength reaches 52kg.cm, and the resin film forming performance is good.

[0106] The above is only a preferred embodiment of the present application, and is not intended to limit the present application in any form. Although the present application has been disclosed as above with a preferred embodiment, it is not intended to limit the present application. Any person skilled in the art can make some changes or modifications to the above disclosed technical content without departing from the scope of the technical solution of the present application, and any equivalent embodiments with equivalent changes and modifications made to the above examples according to the technical essence of the present application are still within the scope of the technical solution of the present application.

Claims

1.A method for synthesizing and applying environmentally friendly solvent-free methyl phenyl silicone resin, comprising the following steps: S1: weighing 100-200 parts of phenyl trimethoxysilane, 750-850 parts of dimethyl carbonate, 80-100 parts of octaphenylcyclotetrasiloxane, and 30-50 parts of a catalyst, and adding them into a reaction kettle, then stirring and heating to react, and filtering the catalyst; S2: heating to 160-180℃ and vacuuming to remove low molecular substances, and then hydrolyzing the obtained product with 300-400 parts of phenyl trimethoxysilane, 80-100 parts of methyl trimethoxysilane, and 50-60 parts of high-purity water, and removing the by-product methanol after hydrolysis to obtain methyl phenyl silicone resin. The reaction temperature of S1 is 80-100℃, and the reaction time is 4-8h. The hydrolysis temperature of S2 is 60-70℃, and the hydrolysis time is 4-6h. The methyl phenyl silicone resin is applied as follows: dissolving 10-20 parts of methyl phenyl silicone resin in 60-80 parts of dimethyl carbonate, filtering, and then brushing the solution on a steel plate, and drying and curing to obtain a resin paint film. The thickness of the paint film is 40-60μm. The curing temperature is 180-200℃, and the curing time is 60-120min. The catalyst is prepared as follows: A1: subjecting a macroporous cationic styrene resin to plasma treatment with 3-mercaptopropionic acid vapor to obtain a mercapto macroporous cationic styrene resin; A2: ultrasonically dispersing 100-200 parts of the mercapto macroporous cationic styrene resin in 1000-1400 parts of ethanol containing 0.2-0.5 parts of methyl allyl tri-n-butyl tin, 3-7 parts of (Z)-9-octadecenoic acid copper (II) salt, and 0.005-0.03 parts of 4-vinylbenzo-18-crown-6 ether-6, adding 0.5-2wt% of a photoinitiator based on the mass percentage of the mercapto macroporous cationic styrene resin, and irradiating under a 230nm-400nm ultraviolet lamp for 30-100min, filtering, washing the product with ethanol, and drying to obtain the catalyst. The photoinitiator is 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone or benzoin dimethyl ether. The plasma treatment device has a treatment time of 30s-90s, a gas flow of 3-mercaptopropionic acid vapor of 10-30sccm, a treatment frequency of 10-15MHz, and a power of 70-80W. ​ ​ 2. The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 1, characterized in that: ​ 3. The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 1, characterized in that: ​ 4. The synthesis method of the environment-friendly solvent-free methylphenyl silicone resin according to claim 1, characterized in that: ​ ​ 5.The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 4, characterized in that: ​ 6. The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 4, characterized in that: ​ 7. The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 1, characterized in that: ​ ​ ​ 8.The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 7, characterized in that: ​ 9.The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 7, characterized in that: ​ 10.The synthesis method and application of the environment-friendly solvent-free methylphenyl silicone resin according to claim 7, characterized in that: The macroporous cationic styrenic resin is selected from D001 or 15 or 35 macroporous cationic styrenic resin.

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