Super-high-temperature-resistant polysiloxane adhesive, preparation method thereof and application of super-high-temperature-resistant polysiloxane adhesive in amorphous strip

Abstract

The invention relates to the technical field of adhesives, in particular to a super-high-temperature-resistant polysiloxane adhesive, a preparation method thereof and application of the super-high-temperature-resistant polysiloxane adhesive in amorphous strips. The silicone rubber composition is prepared from the following raw materials in parts by mass: 50-80 parts of vinyl silicone oil, 15-20 parts of vinyl methyl silicone rubber, 3-5 parts of MQ resin, 1-5 parts of a hydrogen-containing silicone oil cross-linking agent, 0.05-0.1 part of a high-temperature inhibitor, 0.5-1 part of a silane coupling agent, 0.5-0.8 part of a compound silane coupling agent and 0.2-0.5 part of a platinum catalyst. The adhesive disclosed by the invention shows excellent stability in a high-temperature environment, and by optimizing the proportion of the vinyl silicone oil, the vinyl methyl silicone rubber, the MQ resin, the hydrogen-containing silicone oil and the platinum catalyst in the formula, the adhesive can tolerate a high temperature as high as 400 DEG C in a short time, and the long-term use temperature can reach 250 DEG C; the method is suitable for application in the field of amorphous strips (nanocrystalline strips).

Description

Technical Field

[0001] The present invention relates to the technical field of adhesives, and particularly to an ultra-high temperature resistant polyorganosiloxane adhesive, its preparation method and application in amorphous ribbons. Background Art

[0002] With the rapid development of modern industrial technology, the requirements for material properties are increasing day by day. Especially for materials used in high-temperature environments, they need to have excellent heat resistance, mechanical strength, chemical stability and good adhesion properties. Polyorganosiloxane (also known as silicone polymer), as a high-performance polymer material, due to its unique molecular structure (silicon-oxygen bond as the main chain and organic groups as side chains), exhibits excellent stability under harsh conditions such as high temperature, oxidation, and ultraviolet rays, and thus is widely used in fields such as aerospace, electronics, automotive manufacturing, and new energy. However, traditional polyorganosiloxane adhesives still have problems such as insufficient heat resistance and decreased adhesion strength in high-temperature environments, and it is difficult to meet the requirements of some special application scenarios.

[0003] Polyorganosiloxane adhesives are polymer materials with a silicon-oxygen bond as the main chain, and their molecular structure endows the materials with excellent thermal stability, weather resistance and electrical insulation properties. Currently, the research on polyorganosiloxane adhesives mainly focuses on the following aspects: (1) Improvement of high-temperature resistance: By introducing heat-resistant groups such as phenyl and aryl groups, or using crosslinking agents to enhance the crosslinking density between molecular chains to increase the thermal decomposition temperature of the material. (2) Optimization of adhesion performance: By adding functional fillers (such as silica, carbon fiber, etc.) or surface treatment agents to improve the interfacial bonding force between the adhesive and the substrate. (3) Functional expansion: Developing polyorganosiloxane adhesives with special functions such as conductivity, heat conduction, and flame retardancy to meet diverse application requirements.

[0004] Amorphous ribbons are metal materials with an amorphous structure, usually prepared by rapid solidification technology from metals such as iron, nickel, cobalt and non-metallic elements such as silicon and boron. Due to their unique atomic arrangement structure and excellent physical and chemical properties, amorphous ribbons have broad application prospects in fields such as power electronics, magnetic materials, and sensors. In practical applications, amorphous ribbons usually need to be bonded or encapsulated with other materials (such as insulating layers, protective layers or other functional layers), so the selection and application of adhesives are crucial. The adhesive not only needs to provide good adhesion strength, but also needs to meet the performance requirements of amorphous ribbons in harsh environments such as high temperature, high frequency, and high humidity.

[0005] At present, the adhesives applied to amorphous ribbons mainly include the following categories: silicone adhesives, epoxy resin adhesives, polyimide adhesives, acrylate adhesives, etc. Although the polyorganosiloxane adhesive exhibits good stability in the medium temperature range for amorphous ribbons, at high temperatures, its molecular chains are prone to thermal decomposition or oxidation, and the adhesive may lose its bonding strength. The interfacial bonding force between the polyorganosiloxane adhesive and the amorphous ribbon is weak. Especially in high-temperature or humid and hot environments, the bonding strength may be further reduced, resulting in the failure of fixing or encapsulating the amorphous ribbon.

[0006] Certain progress has been made in the research of adhesives for amorphous ribbons, but problems such as insufficient high-temperature resistance and limited interfacial bonding force still exist. Therefore, the development of a super high-temperature resistant polyorganosiloxane adhesive has great application prospects. Summary of the Invention

[0007] The first aspect of the present invention provides an application of a super high-temperature resistant polyorganosiloxane adhesive in amorphous ribbons or nanocrystalline ribbons.

[0008] The second aspect of the present invention provides a super high-temperature resistant polyorganosiloxane adhesive. Calculated by mass, the raw materials for preparation include: 50 - 80 parts of vinyl silicone oil, 10 - 15 parts of vinyl methyl silicone rubber, 3 - 5 parts of MQ resin, 1 - 5 parts of hydrogen-containing silicone oil crosslinking agent, 0.05 - 0.1 part of high-temperature inhibitor, 0.5 - 1 part of silane coupling agent, 0.5 - 0.8 part of compounded silane coupling agent, and 0.2 - 0.5 part of platinum catalyst.

[0009] As a preferred embodiment, the viscosity of the vinyl silicone oil is 1000 - 1500 cps.

[0010] As a preferred embodiment, the crosslinking agent is high-hydrogen-content silicone oil with a hydrogen content of 1.6%.

[0011] As a preferred embodiment, the high-temperature inhibitor includes alkynol inhibitors with a viscosity of 80 - 170 cps.

[0012] As a preferred embodiment, the catalyst includes at least one of chloroplatinic acid and platinum catalyst.

[0013] The present invention uses vinyl silicone oil and vinyl methyl silicone rubber as the main synthetic raw materials, hydrogen-containing silicone oil as the crosslinking agent, and adds chloroplatinic acid catalyst. Under the catalysis of chloroplatinic acid, the vinyl groups in the vinyl silicone oil react with the hydrogen-containing silicone oil through a hydrosilylation reaction to form a stable Si-C bond crosslinked network. By regulating the molar ratio of vinyl silicone oil and hydrogen-containing silicone oil, high crosslinking density can be achieved, forming a tight three-dimensional network structure. The high crosslinking density significantly reduces the thermal motion ability of molecular chains at high temperatures, inhibits the relaxation or slippage of chain segments, thereby delaying high-temperature softening. The siloxane main chain itself has excellent thermal oxidation stability, and the crosslinked network further hinders the diffusion of oxygen, reducing chain scission caused by high-temperature oxidation.

[0014] Through the high-density Si-O-Si / Si-C crosslinked network constructed by the above hydrosilylation reaction, the protective effect of methyl groups, and the efficient catalysis of chloroplatinic acid, the system has achieved a comprehensive improvement in heat resistance at the molecular structure level. Its short-term heat resistance of 400 °C and long-term heat resistance of 250 °C can meet the requirements of amorphous ribbon materials in industrial high-temperature scenarios.

[0015] The third aspect of the present invention provides a method for preparing a super high-temperature resistant polyorganosiloxane adhesive, comprising the following steps:

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] 1. The adhesive of the present invention exhibits excellent stability in high-temperature environments. By optimizing the ratio of vinyl silicone oil and vinyl methyl silicone rubber in the formulation and combining the action of high-temperature inhibitors, the adhesive can withstand high temperatures up to 400 °C in the short term, and the long-term use temperature can reach 250 °C. This high-temperature resistance makes it suitable for bonding requirements in high-temperature working conditions, such as applications in the field of amorphous ribbon materials. In a high-temperature environment, the adhesive will not undergo obvious softening, decomposition, or failure, and can maintain stable bonding strength and structural integrity.

[0018] 2. The adhesive layer formed after curing of the adhesive of the present invention has excellent electrical insulation properties, and its insulation strength can reach more than 15 - 25 kV. This characteristic makes it very suitable for use in the fields of electronics and electricity, such as high-voltage electrical appliances, insulating materials, semiconductor packaging, etc. In a high-voltage environment, the adhesive can effectively prevent current leakage or breakdown, ensuring the safety and reliability of equipment. In addition, its stable chemical structure and high-temperature resistance further enhance its applicability in complex electrical environments.

[0019] 3. The adhesive of the present invention has excellent chemical stability after curing and can withstand the erosion of chemical media such as acids, alkalis, and salts. In addition, its aging resistance is also very prominent, and it is not prone to yellowing, embrittlement, or performance degradation during long-term use. This characteristic makes it suitable for long-term use in outdoor environments or harsh working conditions, such as bonding and sealing in the fields of solar modules, wind power equipment, chemical equipment, etc.

[0020] 4. The adhesive of the present invention uses a high-temperature addition curing reaction. No harmful gases or by-products are generated during the curing process, meeting environmental protection requirements. It can be coated or injected at room temperature and rapidly forms a stable adhesive layer through high-temperature curing. Its fluidity is moderate, making it easy to fill small gaps or complex structures, ensuring the uniformity and integrity of the bonding surface. Detailed implementation mode

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0022] Vinyl silicone oil, purchased from Xin'an Chemical Industry.

[0023] Vinyl methyl silicone rubber, purchased from Hesheng Organosilicon.

[0024] Hydrogen-containing silicone oil, purchased from Jiangxi Bluestar.

[0025] Alkynol inhibitor, purchased from Ospon.

[0026] Compound silane coupling agent, purchased from Dow Corning.

[0027] Example 1

[0028] This example provides an application of a super high-temperature resistant polyorganosiloxane adhesive in amorphous strip or nanocrystalline strip. The super high-temperature resistant polyorganosiloxane adhesive, calculated by mass, the preparation raw materials include: 50 parts of vinyl silicone oil (viscosity 1000 - 1500 cps), 10 parts of vinyl methyl silicone rubber (vinyl content 0.16%), 3 parts of MQ resin, 1 part of hydrogen-containing silicone oil crosslinking agent, 0.05 part of high-temperature inhibitor, 0.5 part of silane coupling agent, 0.5 part of compound silane coupling agent, and 0.2 part of platinum catalyst.

[0029] The crosslinking agent is hydrogen-containing silicone oil.

[0030] The high-temperature inhibitor is an alkynol inhibitor with a viscosity of 80 - 170 cps, specifically ethynyl cyclohexanol.

[0031] The silane coupling agent is silane coupling agent KH-560

[0032] The catalyst is chloroplatinic acid.

[0033] A preparation method of a super high temperature resistant polyorganosiloxane adhesive includes the following steps:

[0034] Put materials according to the ratio, heat the reaction kettle to 180°C under the process, stir with a planetary stirrer, continuously evacuate to remove low-boiling products, keep evacuating under negative pressure to remove toluene solvent, react for 12 hours to obtain the base glue, continuously stir and cool, and discharge through the air release valve.

[0035] Example 2

[0036] This example provides an application of a super high temperature resistant polyorganosiloxane adhesive in amorphous strips or nanocrystalline strips. For the super high temperature resistant polyorganosiloxane adhesive, calculated by mass, the raw materials for preparation include: 80 parts of vinyl silicone oil (viscosity 1000-1500 cps), 20 parts of vinyl methyl silicone rubber (vinyl content 0.16%), 5 parts of fumed silica, 5 parts of crosslinking agent, 0.1 part of high temperature inhibitor, 1 part of silane coupling agent, 0.8 part of polysilane coupling agent, and 0.5 part of catalyst.

[0037] The crosslinking agent is hydrogen-containing silicone oil with a hydrogen content of 1.6%.

[0038] The high temperature inhibitor is an alkynol inhibitor with a viscosity of 80-170 cps, specifically ethynylcyclohexanol.

[0039] The silane coupling agent is silane coupling agent KH-560

[0040] The catalyst is chloroplatinic acid.

[0041] A preparation method of a super high temperature resistant polyorganosiloxane adhesive includes the following steps:

[0042] Put materials according to the ratio, heat the reaction kettle to 180°C under the process, stir with a planetary stirrer, continuously evacuate to remove low-boiling products, keep evacuating under negative pressure to remove toluene solvent, react for 12 hours to obtain the base glue, continuously stir and cool, and discharge through the air release valve.

[0043] Example 3

[0044] This embodiment provides an application of a super high temperature resistant polyorganosiloxane adhesive in amorphous strips or nanocrystalline strips. The super high temperature resistant polyorganosiloxane adhesive, in parts by mass, comprises the following raw materials for preparation: 60 parts of vinyl silicone oil (viscosity 1000 - 1500 cps), 18 parts of vinyl methyl silicone rubber (vinyl content 0.16%), 4 parts of fumed silica, 3 parts of crosslinking agent, 0.07 part of high temperature inhibitor, 0.8 part of silane coupling agent, 0.6 part of polysilane coupling agent, and 0.3 part of catalyst.

[0045] The crosslinking agent is hydrogen-containing silicone oil.

[0046] The high temperature inhibitor is an alkynol inhibitor with a viscosity of 80 - 170 cps, specifically ethynylcyclohexanol.

[0047] The silane coupling agent is silane coupling agent KH-560.

[0048] The catalyst is chloroplatinic acid.

[0049] A preparation method of a super high temperature resistant polyorganosiloxane adhesive comprises the following steps:

[0050] Put the materials according to the ratio, heat the reaction kettle to 180 degrees under the process of the planetary stirrer stirring and reacting, continuously evacuate to remove low-boiling products, keep evacuating under negative pressure to remove toluene solvent, react for 12 hours to obtain the base glue, and discharge through the air release valve after continuously stirring and cooling.

[0051] Performance test

[0052] The polyorganosiloxane adhesives prepared in the above embodiments and comparative examples are subjected to the following tests:

[0053] (1) High temperature resistance test

[0054] The test method includes: baking the test sample at 250 degrees for 48 hours, 300 degrees for 1 hour, 350 degrees for 1 hour, and 400 degrees for 1 hour. There is no decrease in adhesion in the range of 350 degrees and 400 degrees, and the rest of the colloids do not fail.

[0055] (2) Electrical insulation test

[0056] The test results are shown in Table 1.

[0057] Table 1 Performance test results

[0058] Long-term high temperature resistance Short-term high temperature resistance Electrical insulation Example 1 150 °C for 1000 hours 300 °C for 1 hour ≥10 kV Example 2 200 °C for 72 hours 350 °C for 1 hour ≥10 kV Example 3 250 °C for 72 hours 400 °C for 1 hour ≥10 kV

[0059] The above is the preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. Application of an ultra-high temperature resistant polyorganosiloxane adhesive in amorphous ribbons or nanocrystalline ribbons.

2. An ultra-high temperature resistant polyorganosiloxane adhesive according to claim 1, characterized in that: The raw materials for preparation include, by weight: 50-80 parts of vinyl silicone oil, 10-15 parts of vinyl methyl silicone rubber, 3-5 parts of MQ resin, 1-5 parts of hydrogenated silicone oil crosslinking agent, 0.05-0.1 parts of high temperature inhibitor, 0.5-1 parts of silane coupling agent, 0.5-0.8 parts of compounded silane coupling agent, and 0.2-0.5 parts of platinum catalyst.

3. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The viscosity of the vinyl silicone oil is 1000-1500 cps.

4. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The vinyl content of the vinyl methyl silicone rubber is 0.16%.

5. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The cross-linking agent is high hydrogen silicone oil with a hydrogen content of 1.6%.

6. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The high temperature inhibitor includes an acetylene alcohol inhibitor with a viscosity of 80-170 cps.

7. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The viscosity of the polysilane coupling agent is 50-100 cps.

8. The ultra-high temperature resistant polyorganosiloxane adhesive according to claim 2, characterized in that: The catalyst includes at least one of chloroplatinic acid and platinum catalyst.

9. A method for preparing the ultra-high temperature resistant polyorganosiloxane adhesive according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: adding materials according to a proportion, heating the reactor to 180 degrees at a high temperature with a planetary agitator to stir the reaction, continuously evacuating to remove low-boiling point products, maintaining a negative pressure to evacuate to remove the toluene solvent, reacting for 12 hours to obtain a base glue, and continuously stirring and cooling before discharging the material with a gas valve.