CN109796928B

CN109796928B - Organosilicon sealant, device sealed by using organosilicon sealant and application of organosilicon sealant

Info

Publication number: CN109796928B
Application number: CN201910027570.2A
Authority: CN
Inventors: 孙应发; 李海宾; 肖明; 苏丹; 李守平
Original assignee: Beijing Tianshan New Material Technology Co ltd
Current assignee: Beijing Tianshan New Material Technology Co ltd
Priority date: 2019-01-11
Filing date: 2019-01-11
Publication date: 2020-10-16
Anticipated expiration: 2039-01-11
Also published as: CN109796928A; WO2020143714A1

Abstract

The invention relates to an addition type organosilicon sealant, which comprises polyorganosiloxane with unsaturated carbon-carbon double bonds, an inhibitor which is liquid at normal pressure and 0-80 ℃, hydrogen-containing silicone oil and a metal catalyst, and is characterized in that the addition type organosilicon sealant can be solidified when exposed to the atmospheric environment and can not be solidified when not exposed to the atmospheric environment. The part of the addition type organosilicon sealant which is not exposed to the atmospheric environment after being applied can not be solidified, so that the disassembly and repair of equipment are convenient to realize, and the part exposed to the atmospheric environment can be solidified, so that the phenomenon that precipitated oil flows everywhere to influence the appearance of the device is prevented. The invention also relates to a device having one or more sealing surfaces, one or more of which are sealed with an addition silicone sealant. The invention further relates to the use of an addition silicone sealant for sealing the sealing surfaces in the device according to the invention.

Description

Organosilicon sealant, device sealed by using organosilicon sealant and application of organosilicon sealant

Technical Field

The invention relates to the field of organosilicon, in particular to an addition type organosilicon sealant, and also relates to a device for sealing by using the addition type organosilicon sealant and application of the addition type organosilicon sealant.

Background

Many devices require some waterproof and airtight properties, so some parts need to be sealed, such as the flange surface of the insulation basin of the high-voltage switch. At present, substances such as silicone grease, sealing gaskets, condensed type organic silicon sealant, polyurethane and the like are often adopted for sealing similar sealing surfaces. The silicone grease is used for sealing and is easy to disassemble, but because the silicone grease is not solidified, oil is easy to separate in the using process, and the oil can flow at high temperature and further flow out through gaps, so that the sealing effect and the product appearance are influenced. The sealing gasket is used for sealing, a large clamping force is often needed, and due to the limited sealing effect, the sealing gasket is often not used for sealing in occasions with high requirements on sealing performance, such as high-voltage switch sealing, and a layer of silicone grease is required to be smeared on the surface of the sealing gasket or secondary sealing is required to meet the requirements. The sealing performance is realized by using substances such as condensed type organosilicon sealant and polyurethane for sealing and bonding the sealing surface after curing, but when the equipment needs to be disassembled and repaired, the sealant needs to be removed from the sealing surface, and due to the excellent bonding property of the substances, the repairing is difficult.

Disclosure of Invention

In view of the above problems in the prior art and the problems in the prior art discovered by the inventors, the inventors of the present application have conducted extensive research in the field of sealants for sealing surfaces, in order to discover a sealant which is easy to repair and can achieve a good sealing effect, and is particularly suitable for occasions with high sealing requirements. The present inventors have found through their studies that the above object can be achieved by using a specific addition type silicone rubber. After the addition type organosilicon sealant is applied, the organosilicon sealant overflowing from the gap can be exposed in the atmosphere, and the exposed part of the organosilicon sealant can be solidified, so that the addition type organosilicon sealant is sealed between equipment and the solid object, the phenomenon that oil precipitated from the sealant flows everywhere to influence the appearance of the device is prevented, the sealed sealant can not be solidified, and the equipment can be conveniently detached and repaired.

Accordingly, it is an object of the present invention to provide an addition type silicone sealant.

It is a second object of the present invention to provide a device having a sealing surface sealed with an addition silicone sealant.

It is a third object of the present invention to provide the use of the addition type silicone sealant of the present invention for sealing surfaces in the devices of the present invention.

One aspect of the present invention provides an addition type silicone sealant comprising a polyorganosiloxane with an unsaturated carbon-carbon double bond, an inhibitor which is liquid at normal pressure and at a temperature of 0 to 80 ℃, hydrogen-containing silicone oil and a metal catalyst, characterized in that the addition type silicone sealant is solidified when exposed to an atmospheric environment and is not solidified when not exposed to the aforementioned atmospheric environment.

Another aspect of the invention provides a device having one or more sealing surfaces, one or more of which is sealed with an addition silicone sealant, wherein the addition silicone sealant solidifies when exposed to an atmospheric environment and does not solidify when not exposed to the aforementioned atmospheric environment.

In a further aspect of the invention, there is provided the use of an addition type silicone sealant according to the invention for sealing a sealing surface in a device according to the invention.

The invention has the following characteristics:

1. compared with silicone grease, the addition type organosilicon sealant of the invention has no oil bleeding at high temperature, thus not polluting equipment.

2. Compared with a sealing gasket, the addition type organosilicon sealant can meet the sealing requirement without large clamping force.

3. Compared with condensed organosilicon and polyurethane sealant, the addition type organosilicon sealant has the advantages that the sealing part is not solidified, and strong bonding is not formed, so the addition type organosilicon sealant is easy to disassemble and repair.

4. Compared with the traditional addition type organosilicon sealant, the addition type organosilicon sealant disclosed by the invention cannot be solidified under a sealing condition, so that volume shrinkage cannot be generated, micro gaps cannot be generated at an interface, and the sealing effect is not influenced.

Drawings

Fig. 1 shows a cross-sectional view of one embodiment of a sealing device for a battery assembly.

Fig. 2 shows a top view of an embodiment of a sealing device for a battery module with a cover removed.

Figure 3 illustrates a top view of one embodiment of a flange sealing face included in a high voltage switch.

Detailed Description

According to one aspect of the present invention there is provided an addition silicone sealant comprising a polyorganosiloxane having an unsaturated carbon-carbon double bond, an inhibitor which is liquid at ambient pressure and at a temperature of from 0 to 80 ℃, a hydrogen-containing silicone oil and a metal catalyst, characterised in that the addition silicone sealant solidifies when exposed to an atmospheric environment and does not solidify when not exposed to the aforementioned atmospheric environment.

It is noted that in the present invention, the phrase "the addition type silicone sealant will solidify when exposed to the atmospheric environment" means that the surface (or skin) or even all of the portion of the sealant exposed to the atmospheric environment becomes solid due to the formation of a three-dimensional network structure by a crosslinking reaction (i.e., a curing reaction). The solid substance produced has elasticity in atmospheric environment, does not flow, has a fixed shape, and has a certain hardness and tensile modulus. When only the surface (or skin) of the sealant is solidified, the thickness of the resulting solidified article is greater than 0mm, but is usually less than 20mm, preferably 0.5 to 10 mm. The phrase "does not solidify when not exposed to the aforementioned atmospheric environment" means that, when the portion of the sealant exposed to the atmospheric environment solidifies after the sealant of the present invention is applied, the portion of the sealant not exposed to the same atmospheric environment as the aforementioned atmospheric environment (including the same temperature and pressure of the atmosphere) does not become solid, i.e., does not become a solid substance having a three-dimensional network structure.

In the present invention, when the addition type silicone sealant is exposed to an atmospheric environment (i.e., the atmosphere to which the sealant is exposed is open to the atmosphere), the pressure of the atmospheric environment is the pressure of the atmospheric environment itself, typically one atmosphere. In the present invention, when the addition type silicone sealant is exposed to the atmospheric environment, the exposure temperature is not particularly limited, and may be lower than the normal temperature or higher than the normal temperature. For example, the exposure temperature may be as low as 0 ℃ and as high as 200 ℃, such as 10-100 ℃, preferably 80-100 ℃, although normal temperatures are generally also useful.

Under the heating condition, the solidification process is accelerated. Thus, in a preferred embodiment of the invention, one or both of conditions a) and b) satisfy:

a) the addition type organosilicon sealant can solidify within 10 days, preferably within 5 days when exposed to the atmospheric environment at the temperature of 80-100 ℃, and can not solidify within 10 days, preferably within 1 month when not exposed to the atmospheric environment; and

b) the addition type silicone sealants of the present invention solidify within 90 days, preferably within 60 days, when exposed to ambient atmospheric conditions, and do not solidify within 180 days, preferably within 24 months, when not exposed to the aforementioned atmospheric conditions.

The organosilicon sealant is divided into a condensation type sealant and an addition type sealant. The condensed type organosilicon sealant is organosilicon sealant which is obtained by removing micromolecular substances from hydroxyl polyorganosiloxane and an organosilicon crosslinking agent under the action of a catalyst so as to realize crosslinking and curing. The addition type organosilicon sealant is polysiloxane with unsaturated carbon-carbon double bond, and under the action of a catalyst, the carbon-carbon unsaturated double bond is opened to perform addition reaction with hydrogen on silicon atoms in hydrogen-containing silicone oil, so that the cured organosilicon sealant is realized.

In the present invention, polyorganosiloxane having unsaturated carbon-carbon double bonds is used as the base polymer. Generally, the organopolysiloxane backbone is composed in part of repeating units of organo-silicon oxygen bonds, and may have pendant groups (e.g., methyl groups) or side chains on the backbone. The organopolysiloxanes having unsaturated carbon-carbon double bonds can be linear or cyclic, linear organopolysiloxanes being preferred.

According to the invention, the polyorganosiloxane needs to contain unsaturated carbon-carbon double bonds. For this purpose, the polyorganosiloxane may comprise any group bearing an unsaturated carbon-carbon double bond. As the group having an unsaturated carbon-carbon double bond, there may be mentioned an alkenyl group, an acrylate group, and preferably an alkenyl group. As alkenyl there are advantageously used straight-chain or branched alkenyl groups having 2 to 8 carbon atoms or cycloalkenyl groups having 3 to 8 carbon atoms, such as ethenyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, preferably straight-chain or branched alkenyl groups having 2 to 4 carbon atoms, more preferably vinyl.

These groups bearing unsaturated carbon-carbon double bonds are generally bonded to silicon atoms of the polysiloxane backbone, advantageously to terminal silicon atoms of the polysiloxane backbone. The number of unsaturated carbon-carbon double bonds contained in the polyorganosiloxane is usually 2 or more, more preferably 2 to 5 per molecule of the polyorganosiloxane. In a particularly preferred embodiment of the invention, the polyorganosiloxane bearing unsaturated carbon-carbon double bonds is preferably a vinyl-terminated polydimethoxysilane (also known as "vinyl-terminated silicone oil").

Advantageously, the viscosity of the polyorganosiloxanes bearing unsaturated carbon-carbon double bonds is from 100 to 100000 mPas, preferably from 3000 to 30000 mPas.

The addition type organosilicon sealant also comprises hydrogen-containing silicone oil. The hydrogen-containing silicone oil is a cross-linking agent of the addition type silicone sealant, takes repeated Si-O bonds as a main chain and has more than 2, preferably more than 3 hydrogen atoms bonded with silicon atoms in 1 molecule. The hydrogen-containing silicone oil can also be attached with a side group or a side chain on the Si-O main chain. In the present invention, the hydrogen content of the hydrogen-containing silicone oil is favorably 0.1% to 1.2% by weight, preferably 0.15% to 0.5% by weight. The amount of the hydrogen-containing silicone oil is usually 0.15 to 30 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the polyorganosiloxane with an unsaturated carbon-carbon double bond.

The addition type organosilicon sealant comprises an inhibitor. The inhibitor is used for inhibiting the curing reaction of the addition type organosilicon sealant. In the present invention, the inhibitor is in a liquid state at 0 to 80 ℃ under normal pressure, and it is preferable to use an inhibitor in a liquid state at normal temperature and normal pressure. In this context, normal temperature means a temperature of 20 to 25 ℃ and normal pressure means one atmosphere. The molecular weight of the inhibitor is generally 500 or less. As the type of inhibitor, it may be any inhibitor capable of inhibiting the curing reaction of the addition type silicone sealant to form a three-dimensional network structure. In general, the inhibitor may be a compound having a nonmetallic element sharing an electron pair, such as N, P and/or S-containing compounds, and alkenyl and/or alkynyl-containing compounds.

Examples of the N-containing compound include azo compounds and compounds containing one or more of primary amino, secondary amino, tertiary amino, cyano, oxime, nitroso, hydrazine, and O ═ C ═ N —. As the azo compound, azomethane is exemplified. Examples of the compound containing one or more of a primary amino group, a secondary amino group, and a tertiary amino group include tributylamine, triethylamine, diethylamine, N-diethylaminotrimethylsilane, aminotriethoxysilane, and (diisopropylamino) trimethylsilane. The cyano group-containing compound is adiponitrile. As the oxime group-carrying compound, vinyltris (methyl isobutyl ketoximino) silane is exemplified. Examples of the compound having a nitroso group include N-dimethylnitrosamine and N-nitrosodiethylamine. As the compound having a hydrazino group, 2-hydrazinoethanol is exemplified. Examples of the compounds having O ═ C ═ N —, include Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI).

Examples of the P-containing compound include compounds having a phosphate group and/or a phosphine group. Examples of the compound having a phosphate group include triethyl phosphite, triethyl phosphate, and trimethyl phosphate. The phosphine group-containing compound is exemplified by triethylphosphine.

As the S-containing compound, compounds having one or more of the following groups are cited: -S-, sulfone and mercapto. As the compound having-S-are mentioned dimethyl sulfide and ethyl sulfide. As the compound having a sulfone group, thionyl chloride and dimethylsulfoxide can be exemplified. As the compound having a mercapto group, ethanethiol, 2-methyl-3-furanthiol and methanethiol can be mentioned.

As the inhibitor compound having an alkenyl group of the present invention, a compound having one or more of a vinyl group, a maleate group and a fumarate group can be mentioned. As the vinyl group-containing compound, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethyldivinyldisiloxane, dimethoxymethylvinylsilane, and tetramethyltetravinylcyclotetrasiloxane may be mentioned. As the compound having a maleate group, there may be mentioned diallyl maleate, dimethyl maleate, diethyl maleate and dipropyl maleate. As the compound having a fumarate group, monomethyl fumarate, diethyl fumarate and dipropyl fumarate can be mentioned. The alkenyl group-containing silicone compound used as the inhibitor is different from the polyorganosiloxane with an unsaturated carbon-carbon double bond used in the present invention, and the latter is a polymer having a molecular weight of usually 5000 or more, which is much larger than the former.

As said alkynyl group-containing compound, there may be mentioned alkynols such as 3-methyl-1-butyn-3-ol, propargyl alcohol 2-butyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-propyl-butyn-3-ol and 3-octyl-1-butyn-3-ol.

In the present invention, the amount of the inhibitor is usually 1 to 5 parts by mass, preferably 1 to 4 parts by mass, based on 100 parts by mass of the polyorganosiloxane with the unsaturated carbon-carbon double bond. When the amount of the inhibitor exceeds 5 parts by mass, the amount of the metal catalyst to be used is increased, increasing the cost; when the amount of the inhibitor is less than 1 part, the storage stability of the sealant is affected.

The addition type organosilicon sealant also comprises a metal catalyst. The metal catalyst is used for catalyzing addition reaction between polysiloxane with unsaturated carbon-carbon double bonds and hydrogen atoms bonded with silicon atoms in hydrogen-containing silicone oil, so that the organosilicon sealant is converted into a three-dimensional network structure to become a solid, namely, the colloid is solidified. As the type of the metal catalyst, it may be any metal catalyst capable of catalyzing an addition reaction between polyorganosiloxane having an unsaturated carbon-carbon double bond and a hydrogen atom bonded to a silicon atom in hydrogen-containing silicone oil. In the present invention, the metal catalyst may be a platinum catalyst, a rhodium catalyst, or any combination thereof, and is preferably a platinum catalyst. As examples of the platinum catalyst, chloroplatinic acid, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex, bis (ethynyl) (1, 5-cyclooctadiene) platinum complex, bis (ethynyl) (bicyclo [2.2.1] hepta-2, 5-diene) platinum complex, bis (ethynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex, bis (ethynyl) (1, 6-dimethyl-1, 5-cyclooctadiene) platinum complex, diethyl phthalate platinum complex, or any combination thereof may be mentioned. As examples of rhodium catalysts, mention may be made of rhodium chloride, rhodium carbonyl and triphenylphosphine rhodium carbonyl.

The amount of the metal catalyst is favorably 0.001 to 2 parts by mass, preferably 0.1 to 1 part by mass, based on 100 parts by mass of the polyorganosiloxane with the unsaturated carbon-carbon double bond. The dosage of the metal catalyst is not suitable to be too high, and the required inhibition effect can be achieved only by increasing the dosage of the inhibitor, so that the resource waste is caused; if the amount of the metal catalyst is too low, the portion of the sealant colloid exposed to the atmospheric environment is not easily solidified.

The addition type organosilicon sealant of the invention can also contain a filler. The filler can be one or more of aluminum oxide, aluminum hydroxide, magnesium oxide, magnesium hydroxide, silicon micropowder, aluminum nitride, boron nitride, silver powder, calcium carbonate, talcum powder and white carbon black, and the white carbon black is preferred. The amount of the filler may be 1 to 600 parts by mass, preferably 2 to 100 parts by mass, based on 100 parts by mass of the polyorganosiloxane with the unsaturated carbon-carbon double bond.

According to the performance requirements, the addition type organosilicon sealant can also contain pigment, defoaming agent, flame retardant and the like.

The addition type organosilicon sealant can be of a single-component type or a multi-component type. When the sealant is a plurality of components, the catalyst, the hydrogen-containing silicone oil and the polyorganosiloxane with unsaturated carbon-carbon double bonds can not be simultaneously present in the same component, namely, one or two of the three components of the catalyst, the hydrogen-containing silicone oil and the polyorganosiloxane with unsaturated carbon-carbon double bonds need to be separately packaged with the rest of the three components. For ease of handling, the addition silicone sealant of the present invention is preferably a one-pack type.

In accordance with another aspect of the present invention, there is provided a device having one or more sealing surfaces, one or more of which is sealed with an addition silicone sealant, wherein the addition silicone sealant solidifies when exposed to an atmospheric environment and does not solidify when not exposed to the aforementioned atmospheric environment.

It should be noted that after the sealant of the present invention is injected into the sealing surface, a portion of the sealant may be exposed to the atmosphere through the gap (e.g., bolt hole), the sealant exposed to the atmosphere may undergo a cross-linking reaction to form a three-dimensional network structure for solidification, and after solidification occurs, the resulting solid substance having the three-dimensional network structure may isolate the portion of the sealant which is not solidified from the atmosphere, thereby sealing the sealant between the equipment and the solid substance to prevent further solidification. It is noted that solidification tends to occur only in the gel which is exposed to the atmosphere and is present in or flows out of the crevices.

In a preferred embodiment of the device of the present invention, the addition silicone sealant used is an addition silicone sealant of the present invention.

In a preferred embodiment of the device of the present invention, the sealing surface has one or more annular grooves and the addition silicone sealant is located in at least one of the annular grooves. In order to facilitate the introduction of the addition type silicone sealant into the groove, it is advantageous that the bottom of the at least one annular groove and/or the other side opposite to the annular groove is provided with a sealant injection hole. And after the device is assembled, injecting the sealant into the groove through the glue injection hole. The total number of glue injection holes is usually at least 2, and preferably at least 2 glue injection holes are symmetrically distributed relative to the center line of the sealing surface. The centerline refers to an axis perpendicular to the sealing surface. And during glue injection, at least one glue injection hole is reserved for exhausting air in the groove, and after glue injection is finished, the glue injection hole is sealed by a plug.

In a further preferred embodiment of the device according to the invention, the sealing surface has two annular grooves and is arranged side by side on the sealing surface, the groove near the center of the sealing surface being provided with an annular gasket and the groove remote from the center of the sealing surface being filled with an addition silicone sealant. The annular seal is also used to seal against the sealing face.

In a further embodiment of the device according to the invention, the sealing surfaces are additionally fixed by means of one or more of bolts, rivets and welding.

In a further embodiment of the device according to the invention, the sealing surface is a flange sealing surface.

In another embodiment of the invention, the device is a high voltage switch. The sealing surface is a surface needing sealing operation on the high-voltage switch, such as a flange surface sealing surface of an insulating basin and a sealing surface at a pipeline joint.

The device of the present invention may be a sealing device for a battery assembly. One embodiment of the apparatus is shown in figures 1 and 2: fig. 1 is a cross-sectional view of a sealing device for a battery assembly; fig. 2 is a plan view of a sealing device for a battery module with a cover removed. The device comprises a box body 10, a cover body 20 and addition type organic silicon sealant 30, wherein the box body 10 is provided with an accommodating cavity 11 for accommodating a battery. The cover 20 is disposed on the case 10. The first opening 12 of the box 10 has a first flange 13 disposed along the circumferential direction thereof, and the second opening 21 of the cover 20 has a second flange 22 disposed along the circumferential direction thereof. The first flange 13 and the second flange 22 form sealing surfaces of a sealing device for a battery module, and an addition type silicone sealant 30 is interposed between the sealing surfaces to seal the junction of the case body 10 and the cover body 20. The case 10 and the cover 20 are coupled by a fastener 40. Specifically, the fastening member 40 is a bolt and a nut, the first flange 13 has a first mounting hole, the second flange 22 has a second mounting hole, the first mounting hole is opposite to the second mounting hole in axial center, and the bolt passes through the first mounting hole and the second mounting hole, so that the fastening member 40 is connected to the box body 10 and the cover body 20.

The device of the invention can also be a high-voltage switch. An embodiment of one sealing surface of the high-voltage switch is shown in fig. 3. The sealing surface includes a groove 50. The groove 50 has two turns, a first groove 51 away from the center of the seal face and a second groove 52 near the center of the seal face. The first recess 51 includes a plurality of mounting holes 60 and a plurality of glue injection holes 70 therein. The addition type organic silicon sealant is positioned in the first groove 51 to form secondary sealing, and the sealing gasket is positioned in the second groove 52 to form primary sealing.

According to a further aspect of the present invention there is provided the use of an addition type silicone sealant according to the present invention for sealing the sealing face of a device according to the present invention.

By adopting the addition type organic silicon sealant to seal all or part of the sealing surface of the device, the part of the sealant exposed in the atmospheric environment can be solidified, so that the problem of glue flowing can be solved, and the part of the sealant not exposed in the atmospheric environment can not be solidified, so that the sealing surface is easy to disassemble and is easy to clean.

In the present invention, the raw materials used are all commercially available. Unless otherwise specified, the raw materials are used in parts by mass. The numerical range refers to any value in a desirable range, such as 1-30 parts, 10, 10.9, 20 equal parts, and the term "solidified" refers to the fact that the sealant undergoes a crosslinking reaction to form a solid substance with a three-dimensional network structure.

Examples

The present invention will be further described with reference to specific examples. It should be noted that these examples are merely illustrative of the present invention and should not be considered as limiting the scope of the present invention.

Comparative example 1

The kinematic viscosity is 1000mm²100 parts of/s methyl polydimethylsiloxane (201 silicone oil-1000 cp, Jiangxi Star fire organosilicon Co., Ltd.) and 15 parts of fumed silica are stirred in a stirring kettle for 1h, and the product is obtained after gum is produced, wherein the product is silicone grease.

Comparative example 2

The kinematic viscosity is 20000mm²α of/s, 100 parts of omega-dihydroxy polydimethylsiloxane (new safety chemical) and 80 parts of nano calcium carbonate are stirred in a stirring kettle for 30 minutes, then 9 parts of methyltrimethoxysilane is added and stirred for 10 minutes, then 3 parts of fumed silica is added and stirred for 30 minutes, then 0.1 part of gamma-glycidyl ether oxypropyl trimethoxysilane and 0.01 part of dibutyltin diacetate are added and stirred for 10 minutes, and the product is obtained after glue discharging, and is the condensed type organosilicon sealant.

Comparative example 3

The kinematic viscosity is 10000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 303, Runza chemical engineering), 0.01 part of bis (ethynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex, 2 parts of fumaric acid (solid powder), and hydrogen-containing30 parts of hydrogen-containing silicone oil (RH-H6, Runzhe chemical industry) with the amount of 0.1 wt% and 600 parts of alumina are stirred in a stirring kettle for 1.5 hours, and then the silicone sealant is obtained after glue discharging, and is the addition type silicone sealant.

Comparative example 4

The kinematic viscosity is 10000mm²100 parts of vinyl-terminated polydimethylsiloxane (100 parts of (Runza chemical engineering, Vi303), 0.01 part of bis (ethynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex, 0.5 part of diallyl maleate, 30 parts of hydrogen-containing silicone oil (RH-H6) with the hydrogen content of 0.1 wt% and 600 parts of alumina are stirred in a stirring kettle for 1.5 hours, and then the silicone sealant is obtained after glue discharging, and is the addition type silicone sealant.

Example 1

The kinematic viscosity is 100000mm²50 portions of vinyl-terminated polydimethylsiloxane (Vi 301 in Runza chemical industry) with the kinematic viscosity of 100mm ²50 parts of vinyl-terminated polydimethylsiloxane (Vi 321) per second, 2 parts of chloroplatinic acid isopropanol solution of 3000ppm, 5 parts of tetramethyl tetravinylcyclotetrasiloxane, 0.15 part of hydrogen-containing silicone oil (RH-H512) with the hydrogen content of 1.2 wt% and 1 part of fumed silica are stirred in a stirring kettle for 1 hour, and then the silicone sealant is obtained after glue discharging.

Example 2

The kinematic viscosity is 10000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 303, Runza chemical industry), 0.01 part of bis (ethynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex, 1 part of diallyl maleate, 30 parts of hydrogen-containing silicone oil (RH-H6, Runza chemical industry) with the hydrogen content of 0.1 wt% and 600 parts of alumina are stirred in a stirring kettle for 1.5H, and then the silicone sealant is obtained after glue is discharged.

Example 3

The kinematic viscosity is 3000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 333, Runza chemical industry), 0.1 part of diethyl phthalate platinum complex, 2 parts of 3-octyl-1-butyn-3-ol, 5 parts of hydrogen-containing silicone oil (RH-H503) with the hydrogen content of 0.5 wt% and 40 parts of calcium carbonate are stirred in a stirring kettle for 0.5H, and then the organic silicon sealant is obtained after glue discharging.

Example 4

The kinematic viscosity is 20000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 302 in Runza chemical industry), 1 part of diethyl phthalate platinum complex, 4 parts of vinyl trimethoxy silane, 20 parts of hydrogen-containing silicone oil (RH-H33 in Runza chemical industry) with the hydrogen content of 0.18 wt% and 100 parts of calcium carbonate in a stirring kettle, stirring for 1 hour, and discharging to obtain the organic silicon sealant.

Example 5

The kinematic viscosity is 20000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 302 in the field-moistening chemical industry), 2 parts of rhodium chloride, 2 parts of diethylamine, 2 parts of ethanethiol, 20 parts of hydrogen-containing silicone oil (RH-H33 in the field-moistening chemical industry) with the hydrogen content of 0.18 wt% and 100 parts of calcium carbonate are stirred in a stirring kettle for 1 hour, and then the organic silicon sealant is obtained after glue discharging.

Example 6

The kinematic viscosity is 20000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 302 in Runza chemical industry), 1 part of diethyl phthalate platinum complex, 1 part of N-nitrosodiethylamine, 2 parts of triethyl phosphate, 20 parts of hydrogen-containing silicone oil (RH-H33 in Runza chemical industry) with the hydrogen content of 0.18 wt% and 100 parts of calcium carbonate are stirred in a stirring kettle for 1 hour, and then the organic silicon sealant is obtained after glue is discharged.

Example 7

The kinematic viscosity is 20000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 302 in Runza chemical industry), 1 part of diethyl phthalate platinum complex, 1 part of azomethane, 2 parts of 2-hydrazino ethanol, 20 parts of hydrogen-containing silicone oil (RH-H33 in Runza chemical industry) with the hydrogen content of 0.18 wt% and 100 parts of calcium carbonate are stirred in a stirring kettle for 1 hour, and then the organic silicon sealant is obtained after glue is discharged.

Example 8

The kinematic viscosity is 20000mm²100 parts of vinyl-terminated polydimethylsiloxane (Vi 302 in Runza chemical industry), 1 part of diethyl phthalate platinum complex, 1 part of dimethyl sulfide, 2 parts of adiponitrile, 20 parts of hydrogen-containing silicone oil (RH-H33 in Runza chemical industry) with the hydrogen content of 0.5 wt% and 100 parts of calcium carbonate are stirred in a stirring kettle for 1 hour, and then the organic silicon sealant is obtained after glue is discharged.

The sealants prepared according to the respective proportions and the examples are uniformly spread on a No. 45 carbon steel sheet with the thickness of about 1.5-2.5mm in a scraping way, two iron wires with the diameter of 1mm are parallelly placed on a glue layer, the iron wires are perpendicular to the long edges of the steel sheets, then the carbon steel sheets with the same size and type are completely covered on the sealant, and after the carbon steel sheets are tightly pressed, the carbon steel sheets are fixed by a butterfly clamp and are kept still for 30 days at room temperature. The air-exposed portion of the sealant (including the sealant leaking or overflowing around the peripheral edges of the two steel plates) was then observed for solidification. Then placing the mixture in a tray paved with white paper, putting the tray into an oven at 80 ℃, standing for 10 days, and taking out. And observing whether the periphery of the steel sheet has obvious glue overflow or not and the condition of a silicone oil infiltration trace on the white paper, whether the part of the sealant exposed to the air (including the sealant leaked or overflowed from the peripheral edges of the two steel plates) is solidified, whether the internal sealant completely positioned between the two steel plates (namely the part of the sealant not exposed to the air) is solidified, and whether the two steel sheets can be separated by hands. For each example, 5 experiments were performed in parallel and the results are summarized in table 1 below:

according to the experimental results, compared with silicone grease, the sealant disclosed by the invention has the advantages that no bleeding oil flows under the heating condition, and no pollution is caused; compared with the condensed organic silica gel, the disassembly is easy. When fumaric acid, which is an inhibitor that is in a solid state at 0 to 80 ℃ and under normal pressure, is used (comparative example 3), the sealant does not solidify at room temperature or under heating. When the amount of the inhibitor used was too small (comparative example 4), the portion of the addition type silicone sealant which was not exposed to the atmosphere solidified, but since the volume shrinkage occurred after the solidification of the gel, a micro gap was generated between the gel and the sealing surface, and the sealing was not satisfactory.

Claims

1. An addition silicone sealant comprising:

polyorganosiloxane with unsaturated carbon-carbon double bond,

An inhibitor which is liquid at normal pressure and at a temperature of 0-80℃,

Hydrogen-containing silicone oil and

a metal catalyst, a metal oxide catalyst,

characterized in that the addition type organosilicon sealant can be solidified when exposed to the atmospheric environment, but can not be solidified when not exposed to the atmospheric environment, and

the amount of the inhibitor is 1 to 5 parts by mass based on 100 parts by mass of the polyorganosiloxane.

2. The addition silicone sealant according to claim 1, wherein one or both of condition a) and condition b) satisfies:

a) the addition type organosilicon sealant can be solidified within 10 days when exposed to an atmospheric environment at the temperature of 80-100 ℃, and can not be solidified within 10 days when not exposed to the atmospheric environment; and

b) the addition type organosilicon sealant can be solidified within 90 days when exposed to normal temperature atmospheric environment, and can not be solidified within 180 days when not exposed to the atmospheric environment.

3. The addition silicone sealant according to claim 2, wherein one or both of condition a) and condition b) satisfies:

a) the addition type organosilicon sealant can be solidified within 5 days when exposed to an atmospheric environment at 80-100 ℃, and can not be solidified within 1 month when not exposed to the atmospheric environment; and

b) the addition type silicone sealant solidifies within 60 days when exposed to ambient atmospheric conditions, but does not solidify within 24 months when not exposed to the aforementioned atmospheric conditions.

4. The addition silicone sealant according to claim 1 wherein said inhibitor is liquid at ambient temperature and pressure.

5. The addition silicone sealant according to claim 1, wherein the inhibitor is selected from one or more of the group consisting of: compounds containing one or more atoms selected from N, P and S, and organic compounds containing one or more alkenyl and/or one or more alkynyl groups.

6. The addition silicone sealant according to claim 1, wherein the inhibitor is selected from one or more of the group consisting of: azo compounds, alkynols and compounds with one or more of primary, secondary, tertiary, cyano, oxime, nitroso, hydrazine, phosphino, mercapto, -S-, sulfone, phosphate, maleate, fumarate, O ═ C ═ N-, alkynyl and vinyl groups.

7. The addition silicone sealant according to claim 1, wherein the inhibitor is selected from tributylamine, triethylamine, diethylamine, N-diethylaminotrimethylsilylaminotriethoxysilane, (diisopropylamino) trimethylsilane, adiponitrile, vinyltris (methyl isobutyl ketoximino) silane, Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), N-dimethylnitrosamine, N-nitrosodiethylamine, 2-hydrazinoethanol, azomethane, triethyl phosphite, triethyl phosphate, trimethyl phosphate, triethylphosphine, dimethyl sulfide, ethyl sulfide, thionyl chloride, dimethyl sulfoxide, ethanethiol, 2-methyl-3 furanthiol, methanethiol, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethyldivinyldisiloxane, one or more of dimethoxymethylvinylsilane, tetramethyltetravinylcyclotetrasiloxane, diallyl maleate, dimethyl maleate, monomethyl fumarate, diethyl maleate, dipropyl fumarate, 3-methyl-1-butyn-3-ol, propargyl alcohol 2-butyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-propyl-butyn-3-ol and 3-octyl-1-butyn-3-ol.

8. The addition silicone sealant according to claim 2, wherein the inhibitor is tributylamine, triethylamine, diethylamine, N-diethylaminotrimethylsilylaminotriethoxysilane, (diisopropylamino) trimethylsilane, adiponitrile, vinyltris (methyl isobutyl ketoximino) silane, Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), N-dimethylnitrosamine, N-nitrosodiethylamine, 2-hydrazinoethanol, azomethane, triethyl phosphite, triethyl phosphate, trimethyl phosphate, triethylphosphine, dimethyl sulfide, ethyl sulfide, thionyl chloride, dimethyl sulfoxide, ethanethiol, 2-methyl-3 furanthiol, methanethiol, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethyldivinyldisiloxane, One or more of dimethoxymethylvinylsilane, tetramethyltetravinylcyclotetrasiloxane, diallyl maleate, dimethyl maleate, monomethyl fumarate, diethyl maleate, dipropyl fumarate, 3-methyl-1-butyn-3-ol, propargyl alcohol 2-butyn-1-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-propyl-butyn-3-ol and 3-octyl-1-butyn-3-ol.

9. The addition type silicone sealant according to any one of claims 1 to 8, characterized in that the amount of the inhibitor is 1 to 4 parts by mass based on 100 parts by mass of the polyorganosiloxane.

10. The addition silicone sealant according to any of claims 1 to 8, characterized in that the polyorganosiloxane is a vinyl silicone oil.

11. The addition silicone sealant according to claim 10, characterized in that the polyorganosiloxane is a vinyl terminated silicone oil.

12. The addition type silicone sealant according to claim 11, characterized in that the polyorganosiloxane is a vinyl-terminated silicone oil having a viscosity of 100-100000 mpa.s.

13. The addition silicone sealant according to claim 12, characterized in that the polyorganosiloxane is a vinyl terminated silicone oil having a viscosity of 3000-30000 mpa.s.

14. The addition type silicone sealant according to any one of claims 1-8, characterized in that the metal catalyst is a platinum catalyst or a rhodium catalyst or any combination of both.

15. The addition type silicone sealant according to claim 14, characterized in that said metal catalyst is a platinum catalyst.

16. The addition type silicone sealant according to any one of claims 1 to 8, characterized in that the hydrogen content of the hydrogen-containing silicone oil is from 0.1% to 1.2% by weight.

17. The addition type silicone sealant according to claim 16, characterized in that the hydrogen content of said hydrogen-containing silicone oil is 0.15% -0.5% by weight.

18. The addition silicone sealant according to any one of claims 1 to 8, characterized in that one or both of conditions i) and ii) satisfy, based on 100 parts by mass of the polyorganosiloxane:

i) the amount of the hydrogen-containing silicone oil is 0.15-30 parts by mass; and

ii) the amount of the metal catalyst is 0.001 to 2 parts by mass.

19. The addition silicone sealant according to claim 18, characterized in that one or both of conditions i) and ii) satisfy, based on 100 parts by mass of the polyorganosiloxane:

i) the amount of the hydrogen-containing silicone oil is 1-10 parts by mass; and

ii) the amount of the metal catalyst is 0.1 to 1 part by mass.

20. A device having one or more sealing surfaces, one or more of which is sealed with an addition silicone sealant, wherein said addition silicone sealant solidifies when exposed to an atmospheric environment and does not solidify when not exposed to said atmospheric environment, and wherein said addition silicone sealant is an addition silicone sealant according to any one of claims 1-19.

21. A device having one or more sealing surfaces according to claim 20 wherein said sealing surface has one or more annular grooves and said addition silicone sealant is located in at least one of said annular grooves.

22. An apparatus having one or more sealing surfaces according to claim 21 wherein the at least one annular groove has a glue hole in a bottom portion thereof and/or in a side opposite the annular groove.

23. A device having one or more sealing surfaces as claimed in claim 22, wherein the total number of glue injection holes is at least 2.

24. A device according to claim 23, wherein the dispensing holes are arranged symmetrically with respect to the centre line of the sealing surface for at least 2 sealing surfaces.

25. A device according to any one of claims 21 to 24 having one or more sealing surfaces, wherein the sealing surfaces have two annular grooves and are arranged side by side on the sealing surfaces, the groove near the centre of the sealing surfaces having an annular gasket therein and the groove remote from the centre of the sealing surfaces being impregnated with an addition silicone sealant.

26. A device with one or more sealing surfaces according to any of claims 21-24, characterised in that the sealing surfaces are flange sealing surfaces.

27. A device having one or more sealing surfaces according to claim 25 wherein the sealing surfaces are flange sealing surfaces.

28. A device having one or more sealing surfaces according to claim 26, wherein the device is a high voltage switch.

29. Use of the addition silicone sealant according to any one of claims 1 to 17 for sealing surfaces in a device according to any one of claims 20 to 28 with one or more sealing surfaces.