CN111334186A - Room-temperature self-curing insulation coated silica gel and preparation method thereof - Google Patents
Room-temperature self-curing insulation coated silica gel and preparation method thereof Download PDFInfo
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- C09D5/18—Fireproof paints including high temperature resistant paints
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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Abstract
The invention provides a room-temperature self-curing insulation coated silica gel, which comprises the following components in parts by weight: 100 parts of alkoxy-terminated polysiloxane, 0-15 parts of plasticizer, 0-20 parts of fumed silica, 5-20 parts of hollow silica nano microspheres, 0-8 parts of cross-linking agent, 0.5-5 parts of flame retardant and 0.1-3 parts of catalyst; the catalyst is organic titanate or zirconate and chelate thereof. The silica gel has the properties of light weight, room temperature curing, environmental protection, flame retardance and high strength. The invention also provides a preparation method of the room-temperature self-curing insulation coated silica gel.
Description
Technical Field
The invention belongs to the technical field of new organic silicon materials, and particularly relates to room-temperature self-curing insulation coated silica gel and a preparation method thereof.
Background
Power cables are cable products used in the trunk lines of power systems to transmit and distribute high power electrical energy, including various voltage classes, 1-500KV and above, and various insulated power cables. The power transmission line is commonly used for urban underground power grids, leading-out lines of power stations, internal power supply of industrial and mining enterprises and underwater power transmission lines crossing rivers and sea.
The overhead line cable mainly refers to an overhead open line, is erected above the ground and is a power transmission line for transmitting electric energy by fixing a power transmission conductor on a tower erected on the ground through an insulator. The exposed overhead line generally adopts a steel-cored aluminum strand without an insulating protective layer, is convenient to erect and maintain and low in cost, but easily causes accidents in densely populated areas, trees and the like, easily causes electromagnetic interference to the surrounding environment, causes personal and property loss and injury, and therefore, the insulation is imperative.
The organic silicon material has excellent characteristics of high and low temperature resistance, electrical insulation, oxidation resistance stability, weather resistance, hydrophobicity and the like due to the unique structure, and is widely applied to the insulation coating material of the power cable. In addition to the basic characteristics such as high and low temperature resistance, the power cable insulation material must have flame retardancy in view of fire safety, and must also have high strength and light weight in view of sag safety after coating. Earlier patents on wire and cable insulation coating materials abroad, such as application numbers EP19980115880, US19990241474 and the like, disclose different silicone rubber compositions for wire and cable coating protection, which are based on alkenyl-containing polysiloxane polymers and cured by platinum addition or peroxide crosslinking under heating. The heating curing mode is suitable for insulation coating in the production process of wire and cable manufacturers, but is not beneficial to field insulation construction of outdoor overhead bare wires. Room temperature natural curing is an essential requirement for an insulating coating material for convenience of outdoor site construction. Domestic patent like application number 201910347377.7 discloses a room temperature self-curing silica gel insulating material, combines automatic coating robot, can realize automatic construction and open-air, aerial long distance quick automatic coating, and this patent adopts organotin catalysis dealcoholization type cross-linking curing system, has fire-retardant, excellent waterproof sealing performance and anti electric leakage performance. The domestic patents all adopt organic tin catalysts, and need to be improved in the aspect of environmental protection.
Disclosure of Invention
The invention aims to provide room-temperature self-curing insulating coated silica gel and a preparation method thereof.
The invention provides a room-temperature self-curing insulation coated silica gel, which comprises the following raw materials in parts by weight:
the catalyst is organic titanate or zirconate and chelate thereof.
Preferably, the alkoxy-terminated polysiloxane is terminal methyldimethoxy polydimethylsiloxane, and has a structure shown in formula I:
wherein n is an integer of 100 to 1500.
Preferably, the plasticizer is an inert polysiloxane; the inert polysiloxane has a kinematic viscosity of 0.1-50 Pa.s at 25 ℃.
Preferably, the particle size of the hollow silicon dioxide nano-microsphere is 10-80 nm.
Preferably, the crosslinking agent is one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane.
Preferably, the flame retardant is an isocyanurate-containing silane.
Preferably, the flame retardant is 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and/or 1,3, 5-tris (triethoxysilylpropyl) isocyanurate.
Preferably, the catalyst is one or more of isopropyl titanate, isobutyl titanate, tert-butyl titanate, diisopropyl bis (acetoacetato) titanate, diisopropyl bis (acetylacetonato) titanate, n-butyl zirconate chelate and n-propyl zirconate chelate.
Preferably, the specific surface area of the fumed silica is 150-200 m2/g。
The invention provides a preparation method of room-temperature self-curing insulation coated silica gel, which comprises the following steps:
mixing 100 parts by weight of alkoxy-terminated polysiloxane, 0-15 parts by weight of plasticizer, 0-20 parts by weight of fumed silica, 5-20 parts by weight of hollow silica nano microspheres, 0-8 parts by weight of cross-linking agent, 0.5-5 parts by weight of flame retardant and 0.1-3 parts by weight of catalyst, and stirring for 10-60 min under the condition that the vacuum degree is greater than 0.09MPa to obtain room-temperature self-curing insulating coated silica gel;
the catalyst is organic titanate or zirconate and chelate thereof.
The invention provides a room-temperature self-curing insulation coated silica gel, which comprises the following raw materials, by weight, 100 parts of alkoxy-terminated polysiloxane, 0-15 parts of plasticizer, 0-20 parts of fumed silica, 5-20 parts of hollow silica nano-microspheres, 0-8 parts of cross-linking agent, 0.5-5 parts of flame retardant and 0.1-3 parts of catalyst, wherein the catalyst is organic titanate or zirconate and a chelate thereof.
Detailed Description
The invention provides a room-temperature self-curing insulation coated silica gel, which comprises the following raw materials in parts by weight:
the catalyst is organic titanate or zirconate and chelate thereof.
In the present invention, the alkoxy-terminated polysiloxane is preferably a terminal methyldimethoxysilane, having the structure shown in formula I:
wherein n is an integer between 100 and 1500, preferably an integer between 500 and 1000; the viscosity of the alkoxy-terminated polysiloxane at 25 ℃ is preferably 0.8 to 150 pas, more preferably 5 to 130 pas, most preferably 10 to 100 pas, most preferably 20 to 80 pas, most preferably 30 to 50 pas, and specifically 20pas may be used in the embodiment of the present invention.
This patent adopts alkoxy alkyl terminated polysiloxane to replace general α, and omega end hydroxyl polydimethylsiloxane (the common 107 glue on market promptly) uses as the cooperation of basic polymer cooperation titanate catalyst, can effectively avoid the common viscosity peak phenomenon in the single component dealcoholize production process, guarantees to produce smoothly.
In the invention, the plasticizer is preferably inert polysiloxane, more preferably methyl terminated polydimethylsiloxane, and the viscosity of the plasticizer at 25 ℃ is preferably 0.1-50 Pa.s; specifically, in the embodiment of the present invention, it may be 0.3Pa · s. The weight part of the plasticizer is preferably 2 to 12 parts, more preferably 5 to 10 parts, most preferably 8 to 10 parts, and specifically, in an embodiment of the present invention, 10 parts may be used.
In the invention, the fumed silica can be hydrophilic fumed silica or hydrophobic fumed silica, and the specific surface area of the fumed silica is preferably 150-200 m2A concentration of 150 to 180m is more preferable2In particular, in an embodiment of the invention, it may be 150m2The specific surface area of the fumed silica is too high, and the thickening effect is too obvious for the silica gel system in the application, so that the silica gel system is not beneficial to coating. The fumed silica is preferably 2 to 15 parts by weight, more preferably 5 to 10 parts by weight, most preferably 5 to 8 parts by weight, and specifically, in an embodiment of the present invention, 5 parts by weight may be used.
Compared with glass microspheres, the hollow nano silicon dioxide microspheres have smaller particle size and larger specific surface area, can form hydrogen bond reinforcement with a silicone oil main chain, and can form good reinforcement effect while reducing density. The hollow silica nanoparticle is prepared by using a micelle of a triblock polymer polystyrene-polyethylene-PEO structure as a template, using tetraethoxysilane as a precursor, performing sol-gel reaction under an acidic condition, and calcining. In the invention, the particle size of the hollow silicon dioxide nano-microsphere is preferably 10-80 nm, more preferably 20-70 nm, most preferably 30-60 nm, and most preferably 40-50 nm. The weight portion of the hollow silica nanospheres is preferably 5 to 20 parts, more preferably 8 to 15 parts, and most preferably 10 to 12 parts, and specifically, in the embodiment of the present invention, 10 parts may be used.
In the invention, the cross-linking agent is preferably one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane; the weight part of the cross-linking agent is preferably 1 to 7 parts, more preferably 2 to 6 parts, most preferably 3 to 5 parts, and specifically, in the embodiment of the present invention, 5 parts may be used.
In the prior art, because an amino coupling agent has the characteristics of containing polar groups and high activity, the amino coupling agent is often used as a tackifier component and added into single-component silica gel to improve the adhesion of the silica gel to a base material, in the invention, the flame retardant is preferably isocyanurate-containing silane, the isocyanurate silane in the invention can be crosslinked and cured with alkoxy-terminated polydimethylsiloxane to form a net structure which takes Si-O-Si link as a main chain and carbon-nitrogen-containing six-membered rings as side chains, and compared with the simple addition of the isocyanurate with the carbon-nitrogen-containing six-membered rings which cannot participate in reaction, such as triallyl isocyanurate, the heat resistance and flame retardant effect of the insulating coating material can be effectively improved; meanwhile, the chelating reaction between a common tackifier aminosilane coupling agent and a titanate catalyst in the prior art can be avoided, so that the activity of the titanium catalyst is reduced, and the normal curing performance of a silica gel system is ensured. The isocyanurate-containing silane of the present invention is preferably 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and/or 1,3, 5-tris (triethoxysilylpropyl) isocyanurate; the weight part of the flame retardant is preferably 0.5-5 parts, more preferably 1-4 parts, most preferably 2-3 parts, and may also be 0.5-2 parts, specifically, in the embodiment of the present invention, may be 1 part.
In the present invention, the catalyst is preferably organic titanate or zirconate and chelate thereof, more preferably one or more of isopropyl titanate, isobutyl titanate, tert-butyl titanate, diisopropyl bis (acetoacetic acid ethyl ester) titanate, diisopropyl bis (acetylacetone) titanate, n-butyl zirconate chelate and n-propyl zirconate chelate. The weight part of the catalyst is preferably 0.1 to 3 parts, more preferably 0.5 to 2.5 parts, most preferably 1 to 2 parts, and specifically, in the embodiment of the invention, 1 part or 2 parts.
The invention also provides a preparation method of the room-temperature self-curing insulation coated silica gel, which comprises the following steps:
mixing 100 parts by weight of alkoxy-terminated polysiloxane, 0-15 parts by weight of plasticizer, 0-20 parts by weight of fumed silica, 5-20 parts by weight of hollow silica nano microspheres, 0-8 parts by weight of cross-linking agent, 0.5-5 parts by weight of flame retardant and 0.1-3 parts by weight of catalyst, and stirring for 10-60 min under the condition that the vacuum degree is greater than 0.09MPa to obtain room-temperature self-curing insulating coated silica gel;
the catalyst is organic titanate or zirconate and chelate thereof.
Specifically, the alkoxy-terminated polysiloxane, the plasticizer, the fumed silica and the hollow silica nanospheres are preferably placed in a high-speed stirrer and stirred for 10-60 min, preferably 20-50 min, and most preferably 30-40 min under the condition that the vacuum degree is greater than 0.09 MPa; and then adding a cross-linking agent, a flame retardant and a catalyst, and stirring for 10-60 min, preferably 20-50 min, most preferably 30-40 min under the condition that the vacuum degree is more than 0.09MPa to obtain the room-temperature self-curing insulation coated silica gel.
The room temperature self-curing insulation coated silica gel is used as an insulation coating material of a power cable, in particular the power cable in an overhead line.
The invention provides a room-temperature self-curing insulation coated silica gel, which comprises the following raw materials, by weight, 100 parts of alkoxy-terminated polysiloxane, 0-15 parts of plasticizer, 0-20 parts of fumed silica, 5-20 parts of hollow silica nano-microspheres, 0-8 parts of cross-linking agent, 0.5-5 parts of flame retardant and 0.1-3 parts of catalyst, wherein the catalyst is organic titanate or zirconate and a chelate thereof.
In order to further illustrate the present invention, the following examples are provided to describe a room temperature self-curing insulating coated silica gel and a method for preparing the same in detail, but should not be construed as limiting the scope of the present invention.
Example 1
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of 0.3Pa s methyl-terminated polydimethylsiloxane, 5 parts of hydrophobic fumed silica with the specific surface area of 150 and 10 parts of hollow silica microspheres, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then 5 parts of methyltrimethoxysilane, 1 part of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and 1.0 part of diisopropyl bis (ethyl acetoacetate) titanate are added and stirred for 30min under the condition that the vacuum degree is more than 0.09Mpa to prepare the power cable insulation coating silica gel composition which is filled into a rubber tube, and the product performance test result is detailed in table 1.
Example 2
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of 0.3Pa s methyl-terminated polydimethylsiloxane, 5 parts of hydrophobic fumed silica with the specific surface area of 150 and 10 parts of hollow silica microspheres, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then 5 parts of vinyl trimethoxy silane, 1 part of 1,3, 5-tri (triethoxysilylpropyl) isocyanurate and 1.0 part of tert-butyl titanate are added and stirred for 30min under the condition that the vacuum degree is more than 0.09Mpa to prepare the power cable insulation coating silica gel composition which is filled into a rubber tube, and the product performance test result is detailed in table 1.
Example 3
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of 0.3Pa s methyl-terminated polydimethylsiloxane, 5 parts of hydrophobic fumed silica with the specific surface area of 150 and 10 parts of hollow silica microspheres, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then adding 5 parts of phenyltrimethoxysilane, 1 part of 1,3, 5-tri (trimethoxysilylpropyl) isocyanurate and 2.0 parts of n-butyl zirconate chelate, stirring for 30min under the condition that the vacuum degree is greater than 0.09Mpa to prepare the power cable insulation coating silica gel composition, and filling the power cable insulation coating silica gel composition into a rubber hose, wherein the product performance test result is detailed in Table 1.
Comparative example 1
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of 0.3Pa s methyl-terminated polydimethylsiloxane, 10 parts of hydrophobic fumed silica with the specific surface area of 150 and 10 parts of hollow silica microspheres, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then 5 parts of methyltrimethoxysilane and 1.0 part of diisopropyl bis (ethyl acetoacetate) titanate are added and stirred for 30min under the condition that the vacuum degree is more than 0.09Mpa to prepare the power cable insulation coating silica gel composition which is filled into a rubber tube, and the product performance test results are shown in the comparison in Table 1.
Comparative example 2
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of polydimethylsiloxane with 0.3Pa s methyl end capping and 15 parts of hydrophobic fumed silica with the specific surface area of 150, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then 5 parts of methyltrimethoxysilane, 1 part of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and 1.0 part of diisopropyl bis (ethyl acetoacetate) titanate are added and stirred for 30min under the condition that the vacuum degree is more than 0.09Mpa to prepare the power cable insulation coating silica gel composition which is filled into a rubber tube, and the product performance test result is detailed in table 1.
Comparative example 3
100 parts of 20pas end-methyl dimethoxy polydimethylsiloxane; adding 10 parts of 0.3Pa s methyl-terminated polydimethylsiloxane, 5 parts of hydrophobic fumed silica with the specific surface area of 150 and 10 parts of hollow glass microspheres, and stirring for 30min in a high-speed stirrer under the condition that the vacuum degree is greater than 0.09 Mpa; then 5 parts of methyltrimethoxysilane, 1 part of 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and 1.0 part of diisopropyl bis (ethyl acetoacetate) titanate are added and stirred for 30min under the condition that the vacuum degree is more than 0.09Mpa to prepare the power cable insulation coating silica gel composition which is filled into a rubber tube, and the product performance test result is detailed in table 1.
The test method comprises the following steps:
the performance test of the obtained power cable insulation coating silica gel composition is as follows:
1) testing the density of the obtained power cable insulation coating silica gel composition according to the national standard with the standard number GB/T13477.2;
2) testing the hardness of the obtained power cable insulation coating silica gel composition according to the national standard with the standard number GB/T531.1;
3) testing the tensile strength and the elongation at break of the obtained power cable insulation coating silica gel composition according to the national standard with the standard number GB/T528;
4) according to the American flame retardant material standard UL-94: horizontal burning test of B grade and vertical burning test methods of 94V-0, 94V-1 and 94V-2 grade.
According to the performance data of the example 1 and the comparative example 1, the use of the isocyanurate silane can effectively improve the flame retardant effect, and meanwhile, the bonding of aluminum cables is improved; according to the performance data of the example 1 and the comparative example 2, and the comparative example 3 and the performance data, the use of the hollow silica microspheres can simultaneously achieve the effects of effectively reducing the density and keeping the higher mechanical strength.
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.
Claims (10)
1. The room-temperature self-curing insulation coated silica gel comprises the following components in parts by weight:
the catalyst is organic titanate or zirconate and chelate thereof.
2. The room temperature self-curing insulating coated silica gel of claim 1, wherein the alkoxy-terminated polysiloxane is terminal methyldimethoxy polydimethylsiloxane having the structure of formula I:
wherein n is an integer of 100 to 1500.
3. The room temperature self-curing insulating coated silica gel of claim 1 wherein the plasticizer is an inert polysiloxane; the inert polysiloxane has a kinematic viscosity of 0.1-50 Pa.s at 25 ℃.
4. The room temperature self-curing insulation coated silica gel according to claim 1, wherein the hollow silica nanospheres have a particle size of 10-80 nm.
5. The room temperature self-curing insulation coated silica gel according to claim 1, wherein the cross-linking agent is one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
6. The room temperature self-curing insulation coated silica gel of claim 1, wherein said flame retardant is an isocyanurate-containing silane.
7. The room temperature self-curing insulating coated silica gel according to claim 6, wherein the flame retardant is 1,3, 5-tris (trimethoxysilylpropyl) isocyanurate and/or 1,3, 5-tris (triethoxysilylpropyl) isocyanurate.
8. The room temperature self-curing insulation coated silica gel according to claim 1, wherein the catalyst is one or more of isopropyl titanate, isobutyl titanate, t-butyl titanate, diisopropyl bis (acetoacetate) titanate, diisopropyl bis (acetylacetonate) titanate, n-butyl zirconate chelate and n-propyl zirconate chelate.
9. The room temperature self-curing insulating coated silica gel according to claim 1, wherein the fumed silica has a specific surface area of 150 to 200m2/g。
10. A preparation method of room-temperature self-curing insulation coated silica gel comprises the following steps:
mixing 100 parts by weight of alkoxy-terminated polysiloxane, 0-15 parts by weight of plasticizer, 0-20 parts by weight of fumed silica, 5-20 parts by weight of hollow silica nano microspheres, 0-8 parts by weight of cross-linking agent, 0.5-5 parts by weight of flame retardant and 0.1-3 parts by weight of catalyst, and stirring for 10-60 min under the condition that the vacuum degree is greater than 0.09MPa to obtain room-temperature self-curing insulating coated silica gel;
the catalyst is organic titanate or zirconate and chelate thereof.
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| CN113278361A (en) * | 2021-05-14 | 2021-08-20 | 武汉露能科技有限公司 | High-voltage-resistance long-acting stable insulating paint applied to high-voltage power transmission line and preparation method thereof |
| CN115403609A (en) * | 2022-05-09 | 2022-11-29 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of tris [3- (trimethoxysilyl) propyl ] isocyanurate |
| CN115651532A (en) * | 2022-10-28 | 2023-01-31 | 南方电网科学研究院有限责任公司 | Bare conductor insulation coating material and preparation method and application thereof |
| CN116496647A (en) * | 2022-11-11 | 2023-07-28 | 无锡普天铁心股份有限公司 | Insulation coating liquid for surface modification of oriented silicon steel and preparation method thereof |
| CN116836626A (en) * | 2022-03-23 | 2023-10-03 | 江苏天辰新材料股份有限公司 | Room-temperature-cured high-viscosity self-leveling coating and preparation method thereof |
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| CN113278361A (en) * | 2021-05-14 | 2021-08-20 | 武汉露能科技有限公司 | High-voltage-resistance long-acting stable insulating paint applied to high-voltage power transmission line and preparation method thereof |
| CN116836626A (en) * | 2022-03-23 | 2023-10-03 | 江苏天辰新材料股份有限公司 | Room-temperature-cured high-viscosity self-leveling coating and preparation method thereof |
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| CN115651532A (en) * | 2022-10-28 | 2023-01-31 | 南方电网科学研究院有限责任公司 | Bare conductor insulation coating material and preparation method and application thereof |
| CN115651532B (en) * | 2022-10-28 | 2024-01-30 | 南方电网科学研究院有限责任公司 | Bare conductor insulating coating material and preparation method and application thereof |
| CN116496647A (en) * | 2022-11-11 | 2023-07-28 | 无锡普天铁心股份有限公司 | Insulation coating liquid for surface modification of oriented silicon steel and preparation method thereof |
| CN116496647B (en) * | 2022-11-11 | 2024-01-16 | 无锡普天铁心股份有限公司 | Insulation coating liquid for surface modification of oriented silicon steel and preparation method thereof |
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Application publication date: 20200626 |