CN114456604A - Hybrid cross-linked silicone rubber and preparation method thereof - Google Patents
Hybrid cross-linked silicone rubber and preparation method thereof Download PDFInfo
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- CN114456604A CN114456604A CN202210317037.1A CN202210317037A CN114456604A CN 114456604 A CN114456604 A CN 114456604A CN 202210317037 A CN202210317037 A CN 202210317037A CN 114456604 A CN114456604 A CN 114456604A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The invention provides hybrid cross-linked silicone rubber and a preparation method thereof, wherein the hybrid cross-linked silicone rubber is prepared by the following raw material formula in parts by mass through hybrid cross-linking reaction: 100 parts of vinyl polysiloxane, 1-50 parts of vinyl carbon-carbon polymer, 1-400 parts of filler, 1-10 parts of structural control agent, 0.1-5 parts of auxiliary agent and 0.01-3 parts of vulcanizing agent. The hybrid cross-linked silicone rubber of the invention has the advantage of being convenient for adjusting mechanical properties.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to hybrid cross-linked silicone rubber and a preparation method thereof.
Background
With the development of the organic silicon industry in China, China has become a world where the production of organic silicon materials needs to be great. The application of the silicon rubber is particularly wide, and the silicon rubber is applied to various industries of national economy. The silicone rubber is divided into room temperature rubber and high temperature rubber according to the production technical route; they are classified into condensation type, addition type and peroxide vulcanization type according to their crosslinking reaction principles. Wherein the base polymer used in the addition type and peroxide vulcanization type rubber base premix is vinyl polysiloxane. The traditional method has relatively high cost, and the adjustment of the mechanical property of the rubber is realized by selecting the molecular structure and the polymerization degree of the vinyl polysiloxane, selecting different filler matching systems and selecting the variety and the dosage of a vulcanizing agent. With the development of the industry, new breakthroughs in the field are urgently needed from the aspects of cost requirements and technical means for adjusting product performance.
Disclosure of Invention
The invention aims to provide hybrid cross-linked silicone rubber with better cost and more convenient adjustment of mechanical properties and a preparation method thereof.
The embodiment of the invention provides hybrid cross-linked silicone rubber which is prepared by the following raw material formula in parts by mass through hybrid cross-linking reaction: 100 parts of vinyl polysiloxane, 1-50 parts of vinyl carbon-carbon polymer, 1-400 parts of filler, 1-10 parts of structural control agent, 0.1-5 parts of auxiliary agent and 0.01-3 parts of vulcanizing agent.
In the embodiment of the invention, the vinyl polysiloxane is linear polysiloxane or T-type polysiloxane containing at least two terminal vinyl groups or side vinyl groups.
In the embodiment of the invention, the vinyl carbon-carbon polymer is a linear carbon chain polymer or a T-type carbon chain polymer containing more than one terminal vinyl group or side vinyl group, and the number of polymeric chains of the linear carbon chain polymer or the T-type carbon chain polymer is between 10 and 20.
In the embodiment of the invention, the filler is one or more of white carbon black, quartz powder, calcium carbonate powder, aluminum hydroxide, magnesium hydroxide, aluminum oxide, zinc oxide, magnesium oxide, diatomite, montmorillonite and ferric oxide.
In the embodiment of the invention, the structure control agent is polysiloxane or silane with a reactive group at the end.
In the embodiment of the invention, the reactive group is a hydroxyl group or an alkoxy group.
In the embodiment of the invention, the auxiliary agent is one or more of hexamethyldisilazane, water, dimethyldimethoxysilane and diphenyldimethoxysilane.
In the embodiment of the invention, the vulcanizing agent is one of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl 2, 5-di-tert-butyl hexane peroxide.
In the embodiment of the invention, the vulcanizing agent is a platinum complex, the platinum complex is added with methyl hydrogen siloxane at the same time, and the hydrogen mole number of the methyl hydrogen siloxane is 0.3-2 times of the total vinyl mole number in the formula.
The embodiment of the invention also provides a preparation method of the hybrid cross-linked silicone rubber, which comprises the following steps:
uniformly mixing vinyl polysiloxane, vinyl carbon-carbon polymer, filler, a structure control agent and an auxiliary agent to obtain a mixture;
and vacuumizing the obtained mixture to remove gas, cooling to normal temperature, and adding a vulcanizing agent to vulcanize to obtain the hybrid cross-linked silicone rubber.
Compared with the prior art, by adopting the technical scheme of the invention, the vinyl carbon-carbon polymer and the vinyl polysiloxane participate in crosslinking together to form the hybrid silicon rubber inlaid with the carbon-carbon polymer chain segment, which is different from the traditional complete polysiloxane chain, and the cost of the vinyl carbon-carbon polymer is far lower than that of the vinyl polysiloxane, so that the raw material cost of the product is greatly reduced; furthermore, the cross-linking density of the silicon rubber is changed by selecting the vinyl carbon-carbon polymers with different polymerization degrees and different structures, and the purpose of freely adjusting the mechanical property of the silicon rubber is finally achieved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following describes the implementation of the present invention in detail with reference to specific embodiments.
The invention provides hybrid cross-linked silicone rubber which is prepared by the following raw material formula in parts by mass through hybrid cross-linking reaction: 100 parts of vinyl polysiloxane, 1-50 parts of vinyl carbon-carbon polymer, 1-400 parts of filler, 1-10 parts of structural control agent, 0.1-5 parts of auxiliary agent and 0.01-3 parts of vulcanizing agent.
In the embodiment of the invention, the vinyl polysiloxane is linear polysiloxane or T-type polysiloxane containing at least two terminal vinyl groups or side vinyl groups. The vinyl carbon-carbon polymer is a linear carbon chain polymer or a T-type carbon chain polymer containing more than one terminal vinyl group or side vinyl group, and the polymeric chain number of the linear carbon chain polymer or the T-type carbon chain polymer is between 10 and 20. The filler is one or more of white carbon black, quartz powder, calcium carbonate powder, aluminum hydroxide, magnesium hydroxide, aluminum oxide, zinc oxide, magnesium oxide, diatomite, montmorillonite and ferric oxide. The structure control agent is polysiloxane or silane with a reactive group at the end, and the reactive group is hydroxyl or alkoxy. The auxiliary agent is one or more of hexamethyldisilazane, water, dimethyldimethoxysilane and diphenyldimethoxysilane.
In the embodiment of the invention, the vulcanizing agent is one of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, dicumyl peroxide and 2, 5-dimethyl 2, 5-di-tert-butyl hexane peroxide. The vulcanizing agent can also be a platinum complex, the platinum complex needs to be added with methyl hydrogen siloxane at the same time, and the hydrogen mole number of the methyl hydrogen siloxane is 0.3-2 times of the total vinyl mole number in the formula.
Specifically, the preparation method of the hybrid cross-linked silicone rubber comprises the following steps:
uniformly mixing vinyl polysiloxane, vinyl carbon-carbon polymer, filler, a structure control agent and an auxiliary agent to obtain a mixture;
and vacuumizing the obtained mixture to remove gas, cooling to normal temperature, and adding a vulcanizing agent to vulcanize to obtain the hybrid cross-linked silicone rubber.
Two representative examples are described below.
Example 1
In this example, a hybrid cross-linked silicone rubber is provided, which is prepared from the following formulation:
100 parts of methyl vinyl raw rubber (vinyl end capping, the vinyl molar content is 0.05 percent), 10 parts of 907 vinyl resin, 20 parts of precipitated white carbon black (the specific surface area is 200m2/g), 4 parts of hexamethyldisilazane, 0.25 part of distilled water, 4 parts of alpha, omega-dihydroxy polydimethylsiloxane (the polymerization degree is 3-4) and 0.8 part of 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane.
The preparation method of the hybrid cross-linked silicone rubber comprises the following steps:
1) methyl vinyl crude rubber, 907 vinyl resin precipitated white carbon black, hexamethyldisilazane, distilled water and a, omega-dihydroxy polydimethylsiloxane (with the polymerization degree of 3-4) are put into a kneader to be kneaded uniformly, and are reacted for 1-2 hours at the temperature of 110-120 ℃, and then are vacuumized and kneaded for 1 hour, and are stopped to be cooled.
2) After the material in the step 1) is cooled to normal temperature, adding 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, and kneading for 30-60 minutes at normal temperature.
3) Taking the material in the step 2), adding the material into a mold of a hot vulcanizing machine, and carrying out hot-pressing vulcanization at 165 ℃ for 10 min; and then carrying out secondary vulcanization at 200 ℃ for 4h to obtain the hybrid cross-linked silicone rubber.
Example 2
In this example, a hybrid cross-linked silicone rubber is provided, which is prepared from the following formulation:
100 parts of vinyl-terminated methyl polysiloxane (with the viscosity of 350CPS), 200 parts of silicon micropowder (with the mesh size of 1500), 5 parts of 1-octadecene, 1 part of a, omega-dihydroxy-polydimethylsiloxane, 0.05 part of methyltrimethoxysilane, 0.01 part of hexamethyldisilazane, 0.01 part of distilled water, 0.25 part of platinum complex (with the platinum content of 2000PPM) and 5 parts of methyl hydrogen polysiloxane (with the hydrogen content of 1.6%).
The preparation method of the hybrid cross-linked silicone rubber comprises the following steps:
1) vinyl-terminated methyl polysiloxane (viscosity 350CPS), silicon micropowder (1500 meshes), 1-octadecene, alpha, omega-dihydroxy polydimethylsiloxane, methyltrimethoxysilane, hexamethyldisilazane and distilled water are put into a powerful dispersion stirrer and stirred uniformly. Heating to 90 deg.C, stirring for 1 hr, heating to 130 deg.C, and vacuum stirring for 1 hr. Stopping the machine and cooling to normal temperature.
2) Continuously adding the platinum complex and methyl hydrogen polysiloxane, stirring for 3-5 minutes at normal temperature, vacuumizing, and slowly stirring for 3-5 minutes to obtain the rubber material.
3) Taking out the rubber material obtained in the step 2), and storing for 24 hours at normal temperature or heating for 30 minutes at 60 ℃ to obtain the hybrid cross-linked silicone rubber.
In conclusion, by adopting the technical scheme of the invention, the vinyl carbon-carbon polymer and the vinyl polysiloxane participate in crosslinking together to form the hybrid silicon rubber inlaid with the carbon-carbon polymer chain segment, which is different from the traditional complete polysiloxane chain, and the cost of the vinyl carbon-carbon polymer is far lower than that of the vinyl polysiloxane, so that the raw material cost of the product is greatly reduced; furthermore, the cross-linking density of the silicon rubber is changed by selecting the vinyl carbon-carbon polymers with different polymerization degrees and different structures, and the purpose of freely adjusting the mechanical property of the silicon rubber is finally achieved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The hybrid cross-linked silicone rubber is characterized by being prepared from the following raw materials in parts by mass through a hybrid cross-linking reaction: 100 parts of vinyl polysiloxane, 1-50 parts of vinyl carbon-carbon polymer, 1-400 parts of filler, 1-10 parts of structural control agent, 0.1-5 parts of auxiliary agent and 0.01-3 parts of vulcanizing agent.
2. The hybrid cross-linked silicone rubber according to claim 1, wherein the vinyl polysiloxane is a linear polysiloxane or a T-type polysiloxane containing at least two terminal vinyl groups or side vinyl groups.
3. The hybrid cross-linked silicone rubber according to claim 1, wherein the vinyl carbon-carbon polymer is a linear carbon chain polymer or a T-type carbon chain polymer containing more than one terminal vinyl group or side vinyl group, and the polymeric chain number of the linear carbon chain polymer or the T-type carbon chain polymer is between 10 and 20.
4. The hybrid cross-linked silicone rubber according to claim 1, wherein the filler is one or more of white carbon black, quartz powder, calcium carbonate powder, aluminum hydroxide, magnesium hydroxide, aluminum oxide, zinc oxide, magnesium oxide, diatomaceous earth, montmorillonite and iron oxide.
5. The hybrid cross-linked silicone rubber according to claim 1, wherein the structure-controlling agent is a polysiloxane or silane having a reactive group at its end.
6. The hybrid cross-linked silicone rubber according to claim 5, wherein the reactive group is a hydroxyl group or an alkoxy group.
7. The hybrid cross-linked silicone rubber according to claim 1, wherein the auxiliary agent is one or more of hexamethyldisilazane, water, dimethyldimethoxysilane, and diphenyldimethoxysilane.
8. The hybrid cross-linked silicone rubber according to claim 1, wherein the vulcanizing agent is one of benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane.
9. The hybrid cross-linked silicone rubber according to claim 1, wherein the vulcanizing agent is a platinum complex, the platinum complex is added simultaneously with methylhydrogen siloxane, and the hydrogen mole number of the methylhydrogen siloxane is 0.3-2 times of the total vinyl mole number in the formula.
10. The method for preparing a hybrid cross-linked silicone rubber according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing vinyl polysiloxane, vinyl carbon-carbon polymer, filler, a structure control agent and an auxiliary agent to obtain a mixture;
and vacuumizing the obtained mixture to remove gas, cooling to normal temperature, and adding a vulcanizing agent to vulcanize to obtain the hybrid cross-linked silicone rubber.
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| CN202210317037.1A CN114456604A (en) | 2022-03-29 | 2022-03-29 | Hybrid cross-linked silicone rubber and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010011117A1 (en) * | 1997-05-02 | 2001-08-02 | Klaus-Dieter Pesch | Addition crosslinking silicone rubber mixtures, a process for the preparation thereof, a process for the preparation of composite molded parts and the use thereof |
| CN105754349A (en) * | 2016-03-28 | 2016-07-13 | 东莞市贝特利新材料有限公司 | Long-life silicon rubber for peristaltic pump pipes and preparation method of long-life silicon rubber |
| CN109316782A (en) * | 2018-10-01 | 2019-02-12 | 南京瑞思化学技术有限公司 | A kind of preparation and application of modified polyorganosiloxane composition |
| CN110183854A (en) * | 2019-06-03 | 2019-08-30 | 浙江新安化工集团股份有限公司 | A kind of putty type silicone rubber compound and its preparation method and application |
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- 2022-03-29 CN CN202210317037.1A patent/CN114456604A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010011117A1 (en) * | 1997-05-02 | 2001-08-02 | Klaus-Dieter Pesch | Addition crosslinking silicone rubber mixtures, a process for the preparation thereof, a process for the preparation of composite molded parts and the use thereof |
| CN105754349A (en) * | 2016-03-28 | 2016-07-13 | 东莞市贝特利新材料有限公司 | Long-life silicon rubber for peristaltic pump pipes and preparation method of long-life silicon rubber |
| CN109316782A (en) * | 2018-10-01 | 2019-02-12 | 南京瑞思化学技术有限公司 | A kind of preparation and application of modified polyorganosiloxane composition |
| CN110183854A (en) * | 2019-06-03 | 2019-08-30 | 浙江新安化工集团股份有限公司 | A kind of putty type silicone rubber compound and its preparation method and application |
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