阅读说明：本技术 一种复合绝缘涂料及其制备方法和应用 (Composite insulating coating and preparation method and application thereof ) 是由 朱继锋 郑勇明 林伟 凌文 谢思源 李天豪 王长杰 杨丽芳 于 2021-10-09 设计创作，主要内容包括：本申请属于绝缘涂料技术领域,尤其涉及一种复合绝缘涂料及其制备方法和应用。本申请提供了一种复合绝缘涂料及其制备方法和应用；其中,所述复合绝缘涂料包括：有机硅改性丙烯酸乳液、聚酰亚胺溶液、无机填料以及硅烷偶联剂；硅烷偶联剂不仅可以使无机填料与有机硅改性丙烯酸或聚酰亚胺键合,提高了无机填料与有机硅改性丙烯酸或聚酰亚胺的相容性,还利用硅烷偶联剂具有的有机官能基和硅烷氧基,根据相似相溶原理,提高了有机硅改性丙烯酸和聚酰亚胺的相容性,从而使机硅改性丙烯酸乳液,聚酰亚胺溶液,无机填料三者相容性好,提高了复合绝缘材料绝缘性、耐候性,解决了现有技术中复合绝缘涂料绝缘性、耐候性有待提高的技术问题。(The application belongs to the technical field of insulating coatings, and particularly relates to a composite insulating coating and a preparation method and application thereof. The application provides a composite insulating coating and a preparation method and application thereof; wherein the composite insulating coating comprises: organic silicon modified acrylic emulsion, polyimide solution, inorganic filler and silane coupling agent; the silane coupling agent can bond the inorganic filler and the organic silicon modified acrylic acid or polyimide to improve the compatibility of the inorganic filler and the organic silicon modified acrylic acid or polyimide, and also improves the compatibility of the organic silicon modified acrylic acid and polyimide by utilizing the organic functional group and the siloxy group of the silane coupling agent according to the similar intermiscibility principle, so that the compatibility of the organic silicon modified acrylic acid emulsion, the polyimide solution and the inorganic filler is good, the insulating property and the weather resistance of the composite insulating material are improved, and the technical problem that the insulating property and the weather resistance of the composite insulating coating in the prior art need to be improved is solved.)

1. The composite insulating paint is characterized by comprising components of organic silicon modified acrylic emulsion, polyimide solution, inorganic filler and silane coupling agent.

2. The composite insulating paint according to claim 1, wherein the inorganic filler comprises at least one of silica, light calcium powder, mica powder, kaolin, barium sulfate, calcium silicate powder and titanium dioxide.

3. The composite insulating coating of claim 2, wherein the inorganic filler is silica.

4. The composite insulating coating material according to claim 1, wherein the components of the composite insulating coating material comprise, in parts by mass:

10-20 parts of organic silicon modified acrylic emulsion;

5-10 parts of polyimide solution;

20-25 parts of silicon dioxide;

1-2 parts of a silane coupling agent.

5. The composite insulating coating material according to claim 4, wherein the components of the composite insulating coating material comprise, in parts by mass:

15 parts of organic silicon modified acrylic emulsion;

7 parts of polyimide solution;

22 parts of silicon dioxide;

1.5 parts of a silane coupling agent.

6. A method for preparing the composite insulating coating according to any one of claims 1 to 5, characterized in that the preparation method comprises the steps of:

adding a silane coupling agent and a polyimide solution into an organic silicon modified acrylic emulsion, and stirring to obtain a first mixture;

step two: and slowly adding an inorganic filler into the first mixture, and stirring to obtain the composite insulating coating.

7. The method for preparing the composite insulating coating according to claim 6, wherein the method for preparing the organosilicon modified acrylic emulsion comprises the steps of:

injecting 50-70% of acrylic monomer, unsaturated double-bond organic silicon monomer, cross-linking agent, emulsifier and water into a reactor, and stirring to obtain an emulsified product;

dripping 30-50% of acrylic monomer, hydroxyl-terminated polysiloxane and initiator into the emulsified product, and reacting to obtain the organosilicon modified acrylic emulsion;

the reaction temperature is 80-90 ℃;

the reaction time is 2.5-4 h.

8. The method for preparing the composite insulating coating according to claim 7,

the acrylic monomer comprises at least one of acrylic monomer, acrylate monomer and hydroxyl acrylate monomer;

the organosilicon monomer with unsaturated double bonds comprises at least one of vinyl trimethoxy silane, vinyl triethoxy silane and propenyl trimethoxy silane;

the cross-linking agent comprises N-methylene bisacrylamide and/or ethylene glycol diacrylate;

the emulsifier comprises at least one of sodium dodecyl sulfate, alkylphenol polyoxyethylene and propenyl polyoxyethylene;

the initiator includes at least one of 2, 2-azo-bis (2-amidinopropane), benzoyl methyl thiosulfate sodium salt, quaternary ammonium salt type aqueous benzoic acid, and aqueous sulfonate type dimethylbenzone derivative.

9. The method for preparing the composite insulating coating according to claim 7, wherein the components of the silicone-modified acrylic emulsion comprise, in parts by mass:

20-30 parts of unsaturated double-bond organosilicon monomer;

3-5 parts of hydroxyl-terminated polysiloxane;

100 parts of acrylic monomers;

40-60 parts of acrylate monomers;

10-20 parts of hydroxyl acrylate monomers;

0.5-2 parts of a cross-linking agent.

10. Use of the composite insulating coating material according to any one of claims 1 to 5 and the composite insulating coating material prepared by the preparation method according to claims 6 to 9 in the field of weathering.

Technical Field

The application belongs to the technical field of insulating coatings, and particularly relates to a composite insulating coating and a preparation method and application thereof.

Background

The organosilicon modified acrylic resin has the advantages of insulation and weather resistance of organosilicon monomers, and polyimide has excellent insulation performance, so the organosilicon modified acrylic resin and the polyimide resin are common components of composite insulation coatings, such as a water-based organosilicon modified high-hardness hydrophobic UV insulation paint disclosed in CN201811135391.2, a water-based emulsion of acrylic polyester resin modified by hydroxy silicone oil and dimethyl vinyl ethoxy silane is used as matrix resin, and simultaneously vinyl MQ silicone resin which can be cured and can improve hardness and insulation is used as auxiliary material, a high-temperature resistant insulation coating composition disclosed in CN201410503459.3 and a preparation method thereof, wherein the composition comprises epoxy resin, phenolic resin, polyimide resin, zinc borate, trimethylolpropane, benzoyl peroxide, potassium tripolyphosphate, nano titanium dioxide, filler and flame retardant;

however, the organic silicon modified acrylic resin and the polyimide resin are not similar in structure, and the inorganic filler as an inorganic component has poor compatibility with organic components such as organic silicon modified acrylic resin and polyimide resin, so that the insulating property and weather resistance of the organic silicon modified acrylic resin and polyimide in the composite insulating coating can not be fully exerted, and the insulating property and weather resistance of the composite insulating coating need to be improved.

Disclosure of Invention

In view of this, the application provides a composite insulating coating, and a preparation method and an application thereof, which can solve the technical problem that the insulating property and the weather resistance of the composite insulating coating in the prior art need to be improved.

The application provides in a first aspect a composite insulating coating, the components of which comprise: organic silicon modified acrylic emulsion, polyimide solution, inorganic filler and silane coupling agent.

Preferably, the inorganic filler comprises at least one of silicon dioxide, light calcium powder, mica powder, kaolin, barium sulfate, calcium silicate powder and titanium dioxide.

The inorganic filler is silica.

Preferably, the silica is fumed silica.

It should be noted that the fumed silica has a high purity of SiO₂The content is more than 99.8 percent, and a plurality of silicon hydroxyl groups are gathered on the surface of the fumed silica, and the silicon hydroxyl groups have a structure similar to that of siloxane in the organic silicon modified acrylic acid, so that the compatibility of the silica with organic components such as organic silicon modified acrylic resin, polyimide and the like can be further improved.

Preferably, the composite insulating coating comprises the following components in parts by mass:

10-20 parts of organic silicon modified acrylic emulsion;

5-10 parts of polyimide solution;

20-25 parts of silicon dioxide;

1-2 parts of a silane coupling agent.

Preferably, the composite insulating coating comprises the following components in parts by mass:

15 parts of organic silicon modified acrylic emulsion;

7 parts of polyimide solution;

22 parts of silicon dioxide;

1.5 parts of a silane coupling agent.

In a second aspect, the present application provides a method for preparing a composite insulating coating, the method comprising the steps of:

adding a silane coupling agent and a polyimide solution into an organic silicon modified acrylic emulsion, and stirring to obtain a first mixture;

step two: and slowly adding an inorganic filler into the first mixture, and stirring to obtain the composite insulating coating.

Preferably, the preparation method of the organosilicon modified acrylic emulsion comprises the following steps:

injecting 50-70% of acrylic monomer, unsaturated double-bond organic silicon monomer, cross-linking agent, emulsifier and water into a reactor, and stirring to obtain an emulsified product;

dripping 30-50% of acrylic monomer, hydroxyl-terminated polysiloxane and initiator into the emulsified product to obtain the organosilicon modified acrylic emulsion;

the reaction temperature is 80-90 ℃;

the reaction time is 2.5-4 h.

It is to be noted that, a part of reaction monomer reaction monomers such as acrylic acid monomer and the like are added into a reactor for emulsification to obtain an emulsified product, and then the rest reaction monomers and the initiator are added into the emulsified product in a dropwise manner for reaction, so that the conditions that the polymerization reaction is severe due to excessive reaction monomer amount or the initiated polymerization reaction is severe due to excessively high initiator addition speed, and the quality of the polymerized product organosilicon modified acrylic acid emulsion is poor or even the polymerization reaction fails are avoided.

It should be further noted that the reaction time of 2.5-4h includes the time of dropping initiator and the reaction time after dropping initiator, preferably, the time of dropping initiator is 0.5-1h, and the reaction time after dropping initiator is 2-3 h;

preferably, the acrylic monomer comprises at least one of acrylic monomers, acrylate monomers and hydroxyl acrylate monomers;

the organosilicon monomer with unsaturated double bonds comprises at least one of vinyl trimethoxy silane, vinyl triethoxy silane and propenyl trimethoxy silane;

the cross-linking agent comprises N-methylene bisacrylamide and/or ethylene glycol diacrylate;

the emulsifier comprises at least one of sodium dodecyl sulfate, alkylphenol polyoxyethylene and propenyl polyoxyethylene;

the initiator includes at least one of 2, 2-azo-bis (2-amidinopropane), benzoyl methyl thiosulfate sodium salt, quaternary ammonium salt type aqueous benzoic acid, and aqueous sulfonate type dimethylbenzone derivative.

Preferably, the acrylic monomer comprises acrylic acid and/or methacrylic acid;

the acrylic ester monomer comprises at least one of methyl acrylate, ethyl acrylate and butyl acrylate;

the hydroxy acrylic ester monomer comprises methyl hydroxy acrylate and/or ethyl hydroxy acrylate.

Preferably, the silane coupling agent includes at least one of KH550, KH560 and KH 570.

Preferably, the components of the silicone modified acrylic emulsion comprise, by mass:

20-30 parts of unsaturated double-bond organosilicon monomer;

3-5 parts of hydroxyl-terminated polysiloxane;

100 parts of acrylic monomers;

40-60 parts of acrylate monomers;

10-20 parts of hydroxyl acrylate monomers;

0.5-2 parts of a cross-linking agent.

In a third aspect, the application provides a composite insulating coating and an application of the composite insulating coating prepared by the preparation method in the weather-resistant field.

The composite insulating coating provided by the application is added with the curing agent to form a coating, and the components in the composite insulating coating have good compatibility and are not easy to crack, so that the composite insulating coating has excellent insulating property, salt and alkali resistance and the like, and can be suitable for the weather-resistant field.

In summary, the present application provides a composite insulating coating, a preparation method and applications thereof; wherein the composite insulating coating comprises: organic silicon modified acrylic emulsion, polyimide solution, inorganic filler and silane coupling agent; the silane coupling agent has organic functional groups and silane oxygen groups, the silane oxygen groups have reactivity to components such as inorganic fillers, the organic functional groups have reactivity or compatibility to organic silicon modified acrylic emulsion and organic components of polyimide solution, therefore, when the silane coupling agent is between the interfaces of the inorganic components and the organic components, a bonding layer of the organic components, the silane coupling agent and the inorganic components can be formed, so that the inorganic fillers are bonded with organic silicon modified acrylic acid or polyimide, and the compatibility of the inorganic fillers and the organic silicon modified acrylic acid or polyimide is improved;

meanwhile, the structure of the silane oxygen group of the silane coupling agent is similar to that of the siloxane group contained in the organic silicon modified acrylic acid, according to the similar intermiscibility principle, the silane coupling agent and the organic silicon modified acrylic acid have reactivity and compatibility, and the organic functional group and the organic component of polyimide also have reactivity and compatibility, so that the compatibility of the organic silicon modified acrylic acid and the polyimide is improved, the compatibility of the organic silicon modified acrylic acid emulsion, the polyimide solution and the inorganic filler is good, the coating is not easy to crack after being prepared, and the insulativity and the weather resistance of the composite insulating material are improved.

Description of the drawings:

in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.

Fig. 1 is a flow chart of the present application for preparing a composite insulating coating.

The specific implementation mode is as follows:

the application provides a composite insulating coating and a preparation method and application thereof, and can solve the technical problem that the insulating property and the weather resistance of the composite insulating coating in the prior art need to be improved.

The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

The reagents or raw materials used in the following examples are commercially available or self-made.

Example 1

This example 1 provides a preparation method of a first insulating coating, which includes the following steps:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

15g of organic silicon modified acrylic emulsion;

7g of a thermoplastic polyimide solution with a solid content of 20%;

22g of silicon dioxide;

1.5g of silane coupling agent KH550.

Example 2

This example 2 provides a first method for preparing a silicone-modified acrylic emulsion, comprising the steps of:

injecting 60% of first monomer, all unsaturated double-bond organosilicon monomers, cross-linking agent, emulsifier and water into a reactor, adding the rest first monomer, hydroxyl-terminated polysiloxane and initiator into the reactor in a dropwise manner, wherein the dropwise addition time is 0.5-1h, and reacting for 3h after the dropwise addition is finished to finish the reaction;

the first monomer comprises an acrylic monomer, an acrylate monomer and a hydroxyl acrylate monomer.

In the process of preparing the organic silicon modified acrylic emulsion, the addition amount of each component is as follows:

25g of vinyl trimethoxy silane;

4g of a hydroxyl-terminated polysiloxane having a hydroxyl group content of 8%;

100g of acrylic acid;

20g of methyl acrylate;

30g of ethyl acrylate;

15g of methyl hydroxyacrylate;

n, N-Methylenebisacrylamide 1 g;

the emulsifier (sodium lauryl sulfate) corresponds to 2% of the total weight of the monomers;

the initiator (azo initiator) accounts for 0.4% of the total weight of the monomer.

Example 3

This example 3 provides a preparation method of a second insulating paint, which comprises the following steps:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

20g of organic silicon modified acrylic emulsion;

5g of a thermoplastic polyimide solution with a solid content of 20%;

25g of silicon dioxide;

silane coupling agent KH5502 g.

Example 4

This example 4 provides a second method for preparing an organosilicon modified acrylic emulsion, comprising the steps of:

injecting 60% of first monomer, all unsaturated double-bond organosilicon monomers, cross-linking agent, emulsifier and water into a reactor, adding the rest first monomer, hydroxyl-terminated polysiloxane and initiator into the reactor in a dropwise manner, wherein the dropwise addition time is 0.5-1h, and reacting for 3h after the dropwise addition is finished to finish the reaction;

the first monomer comprises an acrylic monomer, an acrylate monomer and a hydroxyl acrylate monomer.

In the process of preparing the organic silicon modified acrylic emulsion, the addition amount of each component is as follows:

30g of vinyltrimethoxysilane;

3g of a hydroxyl-terminated polysiloxane having a hydroxyl group content of 8%;

100g of acrylic acid;

25g of methyl acrylate;

25g of ethyl acrylate;

20g of methyl hydroxyacrylate;

n, N-Methylenebisacrylamide 1.5 g;

the emulsifier (sodium lauryl sulfate) corresponds to 1% of the total weight of the monomers;

the initiator (azo initiator) accounts for 0.5% of the total weight of the monomer.

Example 5

This example 5 provides a preparation method of a third insulating paint, comprising the following steps:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

10g of organic silicon modified acrylic emulsion;

10g of a thermoplastic polyimide solution with a solid content of 20%;

20g of silicon dioxide;

silane coupling agent KH5501 g.

Example 6

This example 6 provides a preparation method of a third silicone-modified acrylic emulsion, comprising the following steps:

injecting 60% of first monomer, all unsaturated double-bond organosilicon monomers, cross-linking agent, emulsifier and water into a reactor, adding the rest first monomer, hydroxyl-terminated polysiloxane and initiator into the reactor in a dropwise manner, wherein the dropwise addition time is 0.5-1h, and reacting for 3h after the dropwise addition is finished to finish the reaction;

the first monomer comprises an acrylic monomer, an acrylate monomer and a hydroxyl acrylate monomer.

In the process of preparing the organic silicon modified acrylic emulsion, the addition amount of each component is as follows:

20g of vinyl trimethoxy silane;

5g of hydroxyl-terminated polysiloxane with 20-30cp and 8 percent of hydroxyl content;

100g of acrylic acid;

40g of methyl acrylate;

15g of methyl hydroxyacrylate;

n, N-Methylenebisacrylamide 0.8 g;

the emulsifier (sodium lauryl sulfate) corresponds to 1% of the total weight of the monomers;

the initiator (azo initiator) accounts for 0.5% of the total weight of the monomer.

Example 7

This example 7 provides a fourth method for preparing an insulating coating, comprising the steps of:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

18g of organic silicon modified acrylic emulsion;

6g of a thermoplastic polyimide solution with a solid content of 20%;

24g of silicon dioxide;

silane coupling agent KH5601 g.

Example 8

This example 8 provides a fourth silicone-modified acrylic emulsion, comprising the steps of:

injecting 60% of first monomer, all unsaturated double-bond organosilicon monomers, cross-linking agent, emulsifier and water into a reactor, adding the rest first monomer, hydroxyl-terminated polysiloxane and initiator into the reactor in a dropwise manner, wherein the dropwise addition time is 0.5-1h, and reacting for 3h after the dropwise addition is finished to finish the reaction;

the first monomer comprises an acrylic monomer, an acrylate monomer and a hydroxyl acrylate monomer.

In the process of preparing the organic silicon modified acrylic emulsion, the addition amount of each component is as follows:

25g of vinyltriethoxysilane;

4g of a hydroxyl-terminated polysiloxane having a hydroxyl group content of 8%;

100g of acrylic acid;

30g of methyl acrylate;

20g of ethyl acrylate;

15g of methyl hydroxyacrylate;

n, N-Methylenebisacrylamide 1 g;

the emulsifier (alkylphenol polyoxyethylene ether: propenyl polyoxyethylene ether ═ 2:1) is 2% of the total weight of the monomers;

the initiator (azo initiator) accounts for 0.4% of the total weight of the monomer.

Example 9

This example 9 provides a fifth preparation method of an insulating coating, including the following steps:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

18g of organic silicon modified acrylic emulsion;

6g of a thermoplastic polyimide solution with a solid content of 20%;

24g of silicon dioxide;

silane coupling agent KH5701 g.

Example 10

This example 10 provides a fifth method for preparing a silicone-modified acrylic emulsion, comprising the steps of:

injecting 60% of first monomer, all unsaturated double-bond organosilicon monomers, cross-linking agent, emulsifier and water into a reactor, adding the rest first monomer, hydroxyl-terminated polysiloxane and initiator into the reactor in a dropwise manner, wherein the dropwise addition time is 0.5-1h, and reacting for 3h after the dropwise addition is finished to finish the reaction;

the first monomer comprises an acrylic monomer, an acrylate monomer and a hydroxyl acrylate monomer.

In the process of preparing the organic silicon modified acrylic emulsion, the addition amount of each component is as follows:

22g of vinyltriethoxysilane;

3.5g of a hydroxyl-terminated polysiloxane having a hydroxyl content of 8%;

100g of acrylic acid;

60g of methyl acrylate;

18g of methyl hydroxyacrylate;

n, N-Methylenebisacrylamide 1 g;

the emulsifier (alkylphenol polyoxyethylene ether: propenyl polyoxyethylene ether ═ 2:1) is 2% of the total weight of the monomers;

the initiator (azo initiator) accounts for 0.4% of the total weight of the monomer.

Example 11

This example 11 provides a sixth method for preparing an insulating coating, comprising the following steps:

the method comprises the following steps: adding a silane coupling agent and a polyimide solution into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

7g of organic silicon modified acrylic emulsion;

15g of a thermoplastic polyimide solution with a solid content of 20%;

22g of silicon dioxide;

1.5g of silane coupling agent KH5501.5g;

the preparation method of the organosilicon modified acrylic emulsion is the same as that of the example 1.

Comparative example 1

This comparative example 1 provides a method for preparing an insulating paint containing no polyimide solution, comprising the steps of:

the method comprises the following steps: adding a silane coupling agent into the organic silicon modified acrylic emulsion and stirring to obtain a mixture;

step two: slowly adding silicon dioxide into the mixture, uniformly dispersing and packaging;

the insulating coating comprises the following components in parts by weight:

22g of organic silicon modified acrylic emulsion;

22g of silicon dioxide;

1.5g of silane coupling agent KH5501.5g;

the preparation method of the organosilicon modified acrylic emulsion is the same as that of the example 1.

Example 12

Example 12 is to examine the properties of the insulating coating materials prepared in example 1, example 11 and comparative example 1.

The insulating coatings prepared in the examples 1 and 11 and the comparative example 1 are coated on a copper substrate, and after the coatings are cured to form films, the hardness, the insulativity, the high temperature resistance and the acid and alkali resistance of the paint films are detected; the detection results are shown in table one.

As can be seen from table one, compared with the composite insulating coating containing both the polyimide solution and the silicone modified acrylic emulsion component disclosed in example 1 or example 11, the composite insulating coating disclosed in comparative example 1 containing the polyimide solution has lower volume resistivity, film hardness, high temperature resistance and acid and alkali resistance than the composite insulating coating containing both the polyimide solution and the silicone modified acrylic emulsion component after being cured into a paint film.

Watch 1

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.