Solvent-free dealcoholization type anti-pollution flashover coating and preparation method thereof

Abstract

The invention discloses a solvent-free dealcoholization type anti-pollution flashover coating and a preparation method of the solvent-free dealcoholization type anti-pollution flashover coating. Comprising the following components in parts by weight: 70-100 parts of polysiloxane, 15-80 parts of filler, 15-60 parts of a flame retardant, 0.3-1 part of a catalyst, 3-10 parts of a curing agent, 2.5-10 parts of a curing accelerator, 1-5 parts of a coupling agent, 3-12 parts of a structure control agent, 0.5-3 parts of a hydroxyl scavenger and 5-70 parts of a reinforcing agent organosilicone modified methoxy MQ silicon resin. According to the anti-pollution flashover coating disclosed by the invention, the addition of zero organic solvent can be realized, the pollution to the environment is reduced, and the corrosion to base materials such as metal is reduced; the anti-pollution flashover coating prepared by the preparation method disclosed by the invention is low in preparation cost and easy to construct, the mechanical property of the anti-pollution flashover coating prepared by the preparation method disclosed by the invention is excellent and can reach 3.52 MPa, the anti-pollution flashover coating has more excellent electrical property and dielectric strength reaching 24.8 KV / mm, and meanwhile, the anti-pollution flashover coating can meet the spraying construction requirement and meets the comprehensive performance requirement of the anti-pollution flashover coating.

Description

Technical Field

[0001] The invention relates to the field of coatings, and in particular to a solvent-free dealcoholization anti-fouling flashover coating and a preparation method thereof. Background Art

[0002] Existing anti-pollution flashover coatings are deketoxime-type anti-pollution flashover coatings prepared based on the film-forming principle of deketoxime small molecules. The removed butanone oxime small molecules are reproductively toxic and are listed as new CMR substances in the EU REACH regulations, which do not meet environmental protection requirements. In addition, traditional anti-pollution flashover coatings use a large amount of organic solvents with a solid content of less than 50%. At present, volatile organic compounds (VOCs) are important raw materials for anti-pollution flashover coatings in the power industry, and room temperature curing anti-pollution flashover coatings are one of the most widely used power protection materials. The organic solvents used are mixtures of alkanes, halogenated hydrocarbons, olefins, aromatic hydrocarbons, etc., accounting for about 30%-70% of the total weight of the coating. They do not participate in the film formation of the coating and are completely evaporated into the atmosphere, causing a large negative impact on the environment. Summary of the invention

[0003] Purpose of the invention: In order to solve the technical problems of the existing anti-pollution flashover coatings, that is, the ketone oxime small molecules are easy to escape and the organic solvents are easy to volatilize and thus harm the environment, the present invention aims to provide a solvent-free dealcoholization anti-pollution flashover coating. The present invention provides a method for preparing the above-mentioned solvent-free dealcoholization anti-pollution flashover coating.

[0004] Technical solution: The solvent-free dealcoholization anti-pollution flashover coating provided by the present invention comprises the following components in parts by mass: 70-100 parts of polysiloxane, 15-80 parts of filler, 15-60 parts of flame retardant, 0.3-1 parts of catalyst, 3-10 parts of curing agent, 2.5-10 parts of curing accelerator, 1-5 parts of coupling agent, 3-12 parts of structure control agent, 0.5-3 parts of hydroxyl scavenger, 5-70 parts of reinforcing agent silicone-modified methoxy MQ silicone resin, preferably 100 parts of polysiloxane, 30-80 parts of filler, 30 parts of flame retardant, 0.5-1 parts of catalyst, 3.5-5 parts of curing agent, 2.5 parts of curing accelerator, 2.75 parts of coupling agent, 3-6 parts of structure control agent, 0.5 parts of hydroxyl scavenger, and 30-70 parts of reinforcing agent silicone-modified methoxy MQ silicone resin.

[0005] Furthermore, the organosilicon is one or both of silazane or vinyl silicone oil, preferably a combination of silazane and vinyl silicone oil; the reinforcing agent organosilicon-modified methoxy MQ silicone resin can greatly improve the mechanical properties of the coating while maintaining the original coating viscosity, thereby improving the defect of insufficient mechanical properties.

[0006] Furthermore, the polysiloxane is a mixture of a high viscosity polysiloxane with a viscosity of 20000-30000 cs, a medium viscosity polysiloxane with a viscosity of 5000-8000 cs and a low viscosity polysiloxane with a viscosity of 200-500 cs in a mass ratio of 1-1.5:2-2.5:3-4. Preferably, the polysiloxane is a mixture of a high viscosity polysiloxane with a viscosity of 20000 cs, a medium viscosity polysiloxane with a viscosity of 5000 cs and a low viscosity polysiloxane with a viscosity of 500 cs in a mass ratio of 1:2:3. Polysiloxanes of different viscosities are mixed in different proportions to reduce the initial viscosity of the base glue. At the same time, the viscosity of the anti-fouling flashover coating is adjusted with the aid of additives such as a structure control agent to achieve the construction conditions for the coating spraying operation.

[0007] Furthermore, the polysiloxane is one or more of terminal hydrogen-containing polysiloxane, terminal methoxyvinyl polysiloxane, terminal methoxy fluorine-containing polysiloxane, and terminal methoxy polydimethyl siloxane, preferably terminal methoxy polydimethyl siloxane.

[0008] Furthermore, the filler is one or more of nano titanium dioxide, iron hydroxide, white carbon black, silicon carbide, aluminum oxide, aluminum nitride, gypsum, boron nitride, silicon carbide, clay, silicon powder, asbestos wool or calcium carbonate, preferably one or two of white carbon black or calcium carbonate; the flame retardant is aluminum hydroxide; the catalyst is one or more of platinum catalyst, titanate or tetramethylammonium hydroxide, preferably tetrabutyl titanate.

[0009] Furthermore, the curing agent is one or more of methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, anilinemethyltrimethoxysilane, diethylaminemethyltrimethoxysilane, and propyltrimethoxysilane, preferably vinyltrimethoxysilane; and the curing accelerator is di-n-hexylamine.

[0010] Furthermore, the coupling agent is one or more of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, preferably a combination of γ-glycidyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

[0011] Furthermore, the structure control agent is one or more of hydroxy silicone oil, diphenylsilanediol, and cyclic trisilazane; and the hydroxy scavenger is caprolactone.

[0012] The present invention provides a method for preparing the above-mentioned solvent-free dealcoholization anti-pollution flashover coating, comprising the following steps:

[0013] (1) dissolving vinyl MQ silicone resin in toluene and chloroplatinic acid, and then dripping trimethoxysilane under heating conditions, stirring, and distilling to obtain methoxy MQ silicone resin; adding organosilicon to the methoxy MQ silicone resin, and after sufficient reaction, obtaining organosilicon-modified methoxy MQ silicone resin;

[0014] (2) adding filler and flame retardant to polysiloxane, stirring, continuing to add structure control agent, stirring to make it completely dispersed, and adding organosilicon-modified methoxy MQ silicone resin prepared in step (1), stirring to obtain a primary mixed rubber;

[0015] (3) adding a curing agent, a curing accelerator, a coupling agent, a catalyst, and a hydroxyl scavenger into the primary mixed rubber, stirring to obtain a composite rubber, and finally filtering to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0016] Furthermore, in step (1), the dosage ratio of the vinyl MQ silicone resin to toluene is 50-80 g:9 mL; the volume ratio of toluene to chloroplatinic acid is 9 mL:100-200 μL; the mass ratio of the vinyl MQ silicone resin to trimethoxysilane is 4-5:1; the mass ratio of the vinyl MQ silicone resin to silicone is 50:1-2; the heating temperature is 65-75°C; and the distillation conditions are: distillation at 100°C for 2-4 hours.

[0017] Principle of the invention: The present invention uses low-viscosity polysiloxane as a matrix, and prepares a solvent-free dealcoholization anti-fouling flashover coating by adding additives such as a curing agent, a catalyst, a filler, a structure control agent, and combining it with an organosilicon-modified methoxy MQ silicone resin reinforcing agent. The dealcoholization anti-fouling flashover coating can still meet the construction conditions required for use under solvent-free conditions, while maintaining good mechanical properties and meeting other properties of the anti-fouling flashover coating. Compared with traditional dealcoholization anti-fouling flashover coatings, it can reduce the volatilization of organic solvents and the production of ketoxime small molecules with reproductive toxicity.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The anti-pollution flashover coating of the present invention can achieve zero addition of organic solvents, reduce pollution to the environment, and reduce corrosion to metal and other substrates; (2) The preparation cost is low and the construction is easy; (3) The anti-pollution flashover coating of the present invention has excellent mechanical properties, which can reach 3.52MPa, and has more excellent electrical properties, with a dielectric strength of 24.8KV / mm. At the same time, it can meet the requirements of spraying construction and meet the comprehensive performance requirements of the anti-pollution flashover coating. DETAILED DESCRIPTION

[0019] The present invention is further described below in conjunction with specific embodiments.

[0020] Example 1: The solvent-free dealcoholization anti-fouling flashover coating provided in this example comprises the following components in parts by mass:

[0021]

[0022] The above-mentioned solvent-free environmentally friendly dealcoholization anti-fouling flashover coating is prepared by the following preparation method:

[0023] (1) Preparation of reinforcing agent: Add 50 g of vinyl MQ silicone resin, 9 ml of toluene and 100 μL of chloroplatinic acid to a 250 ml three-necked flask, then place in a 70° C. aqueous solution, slowly drop 10.9 g of trimethoxysilane, stir for 5 h, and then distill at 100° C. for 2 h to obtain methoxy MQ silicone resin, then drop 0.5 parts of silazane and 0.5 parts of vinyl silicone oil to obtain a silicone-modified methoxymethoxy MQ silicone resin mixture;

[0024] (2) mixing terminal methoxy polydimethylsiloxane with a viscosity of 20000 cs, a viscosity of 5000 cs, and a viscosity of 500 cs in a mass ratio of 1:2:3, stirring, reducing the viscosity of the high-viscosity polysiloxane, and achieving a balance between its viscosity and mechanical properties, and finally obtaining terminal methoxy polydimethylsiloxane with a viscosity of 4500 cs;

[0025] (3) Add filler and flame retardant to the methoxy-terminated polydimethylsiloxane with a viscosity of 4500 cs, stir, continue to add structure control agent, stir for 3-5 minutes to make it completely dispersed, and add the organosilicon-modified methoxy MQ silicone resin prepared in step (1), stir at room temperature for 5-10 minutes to obtain a primary mixed glue;

[0026] (4) Add the curing agent, curing accelerator, coupling agent, catalyst and hydroxyl scavenger to the primary mixed rubber, stir for 3-5 minutes to obtain a composite rubber, and finally filter to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0027] Example 2: The solvent-free dealcoholization anti-fouling flashover coating provided in this example comprises the following components in parts by mass:

[0028]

[0029] The above-mentioned solvent-free environmentally friendly dealcoholization anti-fouling flashover coating is prepared by the following preparation method:

[0030] (1) Add 50 g of vinyl MQ silicone resin, 9 ml of toluene and 100 μL of chloroplatinic acid to a 250 ml three-necked flask, then place in a 70° C. aqueous solution, slowly drop 10.9 g of trimethoxysilane, stir for 5 h, and then distill at 100° C. for 2 h to obtain methoxy MQ silicone resin, then drop 0.5 parts of silazane and 0.5 parts of vinyl silicone oil to obtain silicone-modified methoxy MQ silicone resin;

[0031] (2) mixing terminal methoxy polydimethylsiloxane with a viscosity of 20000 cs, a viscosity of 5000 cs, and a viscosity of 500 cs in a mass ratio of 1:2:3, stirring, reducing the viscosity of the high-viscosity polysiloxane, and achieving a balance between its viscosity and mechanical properties, and finally obtaining terminal methoxy polydimethylsiloxane with a viscosity of 4500 cs;

[0032] (3) Add filler and flame retardant to the methoxy-terminated polydimethylsiloxane with a viscosity of 4500 cs, stir, continue to add structure control agent, stir for 3-5 minutes to make it completely dispersed, and add the organosilicon-modified methoxy MQ silicone resin prepared in step (1), stir at room temperature for 5-10 minutes to obtain a primary mixed glue;

[0033] (4) Add the curing agent, curing accelerator, coupling agent, catalyst and hydroxyl scavenger to the primary mixed rubber, stir for 3-5 minutes to obtain a composite rubber, and finally filter to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0034] Example 3: The solvent-free dealcoholization anti-fouling flashover coating provided in this example comprises the following components in parts by mass:

[0035]

[0036]

[0037] The above-mentioned solvent-free environmentally friendly dealcoholization anti-fouling flashover coating is prepared by the following preparation method:

[0038] (1) Add 50 g of vinyl MQ silicone resin, 9 ml of toluene and 100 μL of chloroplatinic acid to a 250 ml three-necked flask, then place in a 70° C. aqueous solution, slowly drop 10.9 g of trimethoxysilane, stir for 5 h, and then distill at 100° C. for 2 h to obtain methoxy MQ silicone resin, then drop 0.5 parts of silazane and 0.5 parts of vinyl silicone oil to obtain silicone-modified methoxy MQ silicone resin;

[0039] (2) mixing terminal methoxy polydimethylsiloxane with a viscosity of 20000 cs, a viscosity of 5000 cs, and a viscosity of 500 cs in a mass ratio of 1:2:3, stirring, reducing the viscosity of the high-viscosity polysiloxane, and achieving a balance between its viscosity and mechanical properties, and finally obtaining terminal methoxy polydimethylsiloxane with a viscosity of 4500 cs;

[0040] (3) Add filler and flame retardant to the above-mentioned methoxy-terminated polydimethylsiloxane with a viscosity of 4500 cs, stir, continue to add structure control agent, stir for 3-5 minutes to make it completely dispersed, and add the organosilicon-modified methoxy MQ silicone resin prepared in step (1), stir at room temperature for 5-10 minutes to obtain a primary mixed glue;

[0041] (4) Add the curing agent, curing accelerator, coupling agent, catalyst and hydroxyl scavenger to the primary mixed rubber, stir for 3-5 minutes to obtain a composite rubber, and finally filter to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0042] Example 4: The solvent-free dealcoholization anti-fouling flashover coating provided in this example comprises the following components in parts by mass:

[0043]

[0044] The above-mentioned solvent-free environmentally friendly dealcoholization anti-fouling flashover coating is prepared by the following preparation method:

[0045] (1)(1) Add 50 g of vinyl MQ silicone resin, 9 ml of toluene and 100 μL of chloroplatinic acid to a 250 ml three-necked flask, then place in a 70°C aqueous solution, slowly drop 10.9 g of trimethoxysilane, stir for 5 h, and then distill at 100°C for 2 h to obtain methoxy MQ silicone resin, then drop 0.5 parts of silazane and 0.5 parts of vinyl silicone oil to obtain silicone-modified methoxy MQ silicone resin;

[0046] (2) mixing terminal methoxy polydimethylsiloxane with a viscosity of 20000 cs, a viscosity of 5000 cs, and a viscosity of 500 cs in a mass ratio of 1:2:3, stirring, reducing the viscosity of the high-viscosity polysiloxane, and achieving a balance between its viscosity and mechanical properties, and finally obtaining terminal methoxy polydimethylsiloxane with a viscosity of 4500 cs;

[0047] (3) Add filler and flame retardant to the above-mentioned methoxy-terminated polydimethylsiloxane with a viscosity of 4500 cs, stir, continue to add structure control agent, stir for 3-5 minutes to make it completely dispersed, and add the organosilicon-modified methoxy MQ silicone resin prepared in step (1), stir at room temperature for 5-10 minutes to obtain a primary mixed glue;

[0048] (4) Add the curing agent, curing accelerator, coupling agent, catalyst and hydroxyl scavenger to the primary mixed rubber, stir for 3-5 minutes to obtain a composite rubber, and finally filter to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0049] Example 5: The solvent-free dealcoholization anti-fouling flashover coating provided in this example comprises the following components in parts by mass:

[0050]

[0051] The above-mentioned solvent-free environmentally friendly dealcoholization anti-fouling flashover coating is prepared by the following preparation method:

[0052] (1) Add 50 g of vinyl MQ silicone resin, 9 ml of toluene and 100 μL of chloroplatinic acid to a 250 ml three-necked flask, then place in a 70° C. aqueous solution, slowly drop 10.9 g of trimethoxysilane, stir for 5 h, and then distill at 100° C. for 2 h to obtain methoxy MQ silicone resin, then drop 0.5 parts of silazane and 0.5 parts of vinyl silicone oil to obtain the final modified silicone-modified methoxy MQ silicone resin mixture;

[0053] (2) mixing terminal methoxy polydimethylsiloxane with a viscosity of 20000 cs, a viscosity of 5000 cs, and a viscosity of 500 cs in a mass ratio of 1:2:3, stirring, reducing the viscosity of the high-viscosity polysiloxane, and achieving a balance between its viscosity and mechanical properties, and finally obtaining terminal methoxy polydimethylsiloxane with a viscosity of 4500 cs;

[0054] (3) Add filler and flame retardant to the above-mentioned methoxy-terminated polydimethylsiloxane with a viscosity of 4500 cs, stir, continue to add structure control agent, stir for 3-5 minutes to make it completely dispersed, and add the organosilicon-modified methoxy MQ silicone resin prepared in step (1), stir at room temperature for 5-10 minutes to obtain a primary mixed glue;

[0055] (4) Add the curing agent, curing accelerator, coupling agent, catalyst and hydroxyl scavenger to the primary mixed rubber, stir for 3-5 minutes to obtain a composite rubber, and finally filter to obtain a solvent-free dealcoholization anti-fouling flashover coating.

[0056] Comparative Example 1: The difference from Example 3 is that no reinforcing agent is included, and the preparation method is the same as that of Example 3.

[0057] Comparative Example 2: The difference from Example 3 is that the weight fraction of the reinforcing agent is 90 parts.

[0058] Comparative Example 3: The difference from Example 3 is that the reinforcing agent is methoxy MQ silicone resin.

[0059] The performance of the anti-fouling flashover coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was tested, and the results are shown in Table 1 below.

[0060] Table 1 Experimental data of Example 1-Example 5 and Comparative Example 1-Comparative Example 3

[0061]

[0062] As can be seen from Table 1, in Example 1, 20 parts of modified silicone methoxy MQ silicone resin are added on the basis of conventional white carbon black reinforcement, and its mechanical properties reach the tensile strength requirement of 3MPa close to that in DL 627-2018, while the dielectric strength and elongation at break meet the requirements, and the viscosity of coating 4 is 90 seconds, which meets the requirements of construction spraying; in Example 2, the mass parts of modified silicone methoxy MQ silicone resin and white carbon black are reduced, and calcium carbonate is additionally added as reinforcement, and the performance is close to that of Example 1, but the tensile strength does not meet the requirements of DL 627-2018; in Example 3, on the basis of Example 1, the mass parts of white carbon black and silicone methoxy MQ silicone resin are increased at the same time, and the reinforcement effect is obvious. While meeting the requirements of lower viscosity of coating 4, the requirements of strength, dielectric and elongation are met at the same time; in Examples 4 and 5, on the basis of Example 1, the mass parts of modified silicone methoxy MQ silicone resin are increased to different degrees, and the results all meet the standards and construction requirements. In Comparative Examples 1 and 2, no reinforcing agent was added or an excessive amount of reinforcing agent was added, which would result in a decrease in the hardness and tensile strength of the coating. In Comparative Example 3, the coating with an unmodified reinforcing agent also had a low tensile strength.

Claims

1. A solvent-free dealcoholization anti-fouling flashover coating, characterized in that: The invention comprises the following components by mass: 70-100 parts of polysiloxane, 15-60 parts of filler, 15-80 parts of flame retardant, 0.3-1 parts of catalyst, 3-10 parts of curing agent, 2.5-10 parts of curing accelerator, 1-5 parts of coupling agent, 3-12 parts of structure control agent, 0.5-3 parts of hydroxyl scavenger and 5-70 parts of reinforcing agent organosilicon-modified methoxy MQ silicone resin.

2. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The organosilicon is one or both of silazane and vinyl silicone oil.

3. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The polysiloxane is a mixture of high-viscosity polysiloxane with a viscosity of 20000-30000 cs, medium-viscosity polysiloxane with a viscosity of 5000-8000 cs and low-viscosity polysiloxane with a viscosity of 200-500 cs in a mass ratio of 1-1.5:2-2.5:3-4.

4. The solvent-free dealcoholization anti-fouling flashover coating according to claim 3, characterized in that: The polysiloxane is one or more of terminal hydrogen-containing polysiloxane, terminal methoxyvinyl polysiloxane, terminal methoxy fluorine-containing polysiloxane, and terminal methoxy polydimethylsiloxane.

5. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The filler is one or more of nano titanium dioxide, iron hydroxide, white carbon black, silicon carbide, aluminum oxide, aluminum nitride, gypsum, boron nitride, silicon carbide, clay, silicon micropowder, asbestos wool or calcium carbonate; the flame retardant is aluminum hydroxide; and the catalyst is one or more of platinum catalyst, titanate or tetramethylammonium hydroxide.

6. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The curing agent is one or more of methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, anilinemethyltrimethoxysilane, diethylaminemethyltrimethoxysilane and propyltrimethoxysilane; the curing accelerator is di-n-hexylamine.

7. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The coupling agent is one or more of γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane.

8. The solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The structure control agent is one or more of hydroxy silicone oil, diphenylsilanediol, and cyclic trisilazane; and the hydroxy scavenger is caprolactone.

9. A method for preparing the solvent-free dealcoholization anti-fouling flashover coating according to claim 1, characterized in that: The following steps are involved: (1) dissolving vinyl MQ silicone resin in toluene and chloroplatinic acid, and then dripping trimethoxysilane under heating conditions, stirring, and distilling to obtain methoxy MQ silicone resin; adding silicone to the methoxy MQ silicone resin, and after sufficient reaction, obtaining reinforcing agent silicone-modified methoxy MQ silicone resin; (2) adding filler and flame retardant to polysiloxane, stirring, continuing to add structure control agent, stirring to make it completely dispersed, and adding reinforcing agent organosilicon-modified methoxy MQ silicone resin prepared in step (1), stirring to obtain a primary mixed rubber; (3) adding a curing agent, a curing accelerator, a coupling agent, a catalyst, and a hydroxyl scavenger into the primary mixed rubber, stirring to obtain a composite rubber, and finally filtering to obtain a solvent-free dealcoholization anti-fouling flashover coating.

10. The preparation method according to claim 9, characterized in that: In step (1), the amount ratio of the vinyl MQ silicone resin to toluene is 50-80 g:9 mL; the volume ratio of toluene to chloroplatinic acid is 9 mL:100-200 μL; the mass ratio of the vinyl MQ silicone resin to trimethoxysilane is 4-5:1; the mass ratio of the vinyl MQ silicone resin to silicone is 50:1-2; the heating temperature is 65-75°C; and the distillation conditions are: distillation at 100°C for 2-4 hours.

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