CN105255197A - Silicone rubber nano composite with high tear resistance and preparation method thereof - Google Patents
Silicone rubber nano composite with high tear resistance and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicone rubber nano composite with the high tear resistance. The composite is prepared from, by weight, 100 parts of silicone rubber, 3-10 parts of carbon nano tubes, 30-50 parts of fumed silica, 3-6 parts of hydroxyl silicone oil, 0.5-3.5 parts of vulcanizing agents and 0.2-0.8 part of interface agents. According to the silicone rubber nano composite with the high tear resistance and the preparation method thereof, by selecting and using the interface agents, the problems that when the carbon nano tubes serve as reinforcing fillers, the carbon nano tubes are unevenly dispersed in the silicone rubber, and the interfacial action of the carbon nano tubes and the silicone rubber is weak are solved, and the tearing property of the silicone rubber nano composite is significantly improved.
Description
Technical field
The present invention relates to a kind of High tear resistance silicon rubber nano-complex and preparation method thereof, belong to silicon rubber technical field.
Background technology
Silicon rubber is the linear polysiloxane macromolecular elastomer that main chain is made up of-Si-O-, side chain is made up of organic group, because the main chain of its uniqueness forms, make it have the advantages such as high-low temperature resistant, resistance to ozone, radiation hardness, electrical insulating property, good biocompatibility, highly air-permeable, physiological inertia, so silicon rubber is used for the fields such as aerospace, chemical instruments, agricultural, health care and electronic apparatus industry.But the intensity of silicon rubber is very poor, and especially tear strength is very poor, greatly limit the application of silicon rubber.Therefore improve the intensity of silicon rubber, especially tear strength, make the mechanical property of silicon rubber reach service requirements, become the focus of research and development silicone rubber products both at home and abroad.
In patent CN101157801A, discuss a kind of highly ripping-resistant high temperature sulfidation silicon rubber and preparation method thereof, it is characterized in that: make rubber composition by the silicon rubber of high-vinyl-content and low vinyl content is carried out kneading, make it in sulfidation, produce uneven Concentrative crosslinking, make stress dispersion, thus improve the tear strength of silastic product.The way adopting Concentrative crosslinking equally, quick the discussing of Li Zhi adds t etram-ethyltetravinylcyclotetrasiloxane as Concentrative crosslinking agent in silicon rubber, in sulfidation, producing Concentrative crosslinking, (Li Zhi is quick to improve the tear strength of silicon rubber, Wu Youping " preparation of high tear silicon rubber composite material ", China Synthetic Rubber Industry, 2015-03-15,38 (2): 141-144).
The carbocyclic ring that carbon nanotube is made up of six carbon forms, stronger reactive force is had between carbon nanotube, so carbon nanotube is difficult to dispersed in the base, again because carbon nano tube surface lacks active group, so the reactive force between carbon nanotube and matrix is very weak, there is dispersion ununiformity and and the weak shortcoming of basal body interface effect all the time adding in rubber matrix in carbon nanotube.Sui Gang adopts mixing acid process carbon nanotube, in the reunion that carbon nano tube surface introduces hydroxyl, carboxyl improves carbon nanotube and the weak shortcoming of natural gum interface interaction.(Sui Gang, Liang Ji, Zhu Yuefeng, Yang little Ping " Structure and Properties of Carbon Nanotubes/natural Rubber Composites ", China Synthetic Rubber Industry, 2005-01-15,28 (1): 40 ~ 43).
Relatively existing technology, advantage of the present invention is: both do not adopted Concentrative crosslinking to improve the tear strength of silicon rubber, does not also adopt the blended tear strength improving silicon rubber of the silicon rubber of different contents of ethylene.The present invention adopts interfacial agents to solve the dispersion problem of carbon nanotube in rubber matrix and interface compatibility problem.At high temperature, this interfacial agents can be decomposed into the free radical containing phenyl ring, and this free radical one side and carbon nanotube have π-πconjugation, thus promote the dispersing uniformity of carbon nanotube in rubber matrix, stop the secondary agglomeration of carbon nanotube; This free radical participates in the cross-linking process of silicon rubber on the other hand, carbon nanotube and silicon rubber are linked together by interfacial agents, thus the interface compatibility improved between carbon nanotube and silicon rubber, increase substantially the tear strength of silicon rubber, and the silastic product of preparation has excellent heat conduction and conductivity simultaneously, preparation is simple.
Summary of the invention
The present invention breaks the method for existing raising silicon rubber tear strength, provides a kind of method that can increase substantially silicon rubber tear strength.
To achieve these goals, the present invention adopts following technical scheme, by weight, comprises following composition:
100 parts, silicon rubber, the molar fraction 0.05%-5% of vinyl, number-average molecular weight 300000-1000000, carbon nanotube 3-10 part, thermal silica 30-50 part, hydroxy silicon oil 3-6 part, vulcanizing agent 0.5-3.5 part, interfacial agents 0.2-0.8 part.
In addition, the present invention also provides following attached technical scheme:
(1) the vinyl molar fraction of described vinylsiloxane rubber is 0.05%-5%, preferred 0.1-0.3%, and molecular weight is 300000-1000000, preferred 400000-60000.
(2) described interfacial agents comprises tetra-benzyl thiram disulfide, dimethyl diphenylthiuram disulfide, diethyl diphenyl thiuram disulfide, dibenzothiazyl disulfide, methylenediphenyl diamines, dibenzyl amine, preferred tetra-benzyl thiram disulfide, preferred tetra-benzyl thiram disulfide is because it contains four phenyl ring, and the effect of carbon nanotube is stronger.
(3) described peroxide comprises benzoyl peroxide, 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexanes, dicumyl peroxide, preferably 2,5-dimethyl-2,5-bis(t-butylperoxy) hexanes.
A kind of preparation technology's flow process of this silicon rubber of high resistance is:
The silicon rubber of 100g contents of ethylene 0.05%-5%, molecular weight 300000-8000000 is placed in the mill of room temperature, after stablizing bag roller, add interfacial agents 0.2-0.8 part, carbon nanotube 3-10 part, thermal silica 30-50 part, hydroxy silicon oil 3-6 part, vulcanizing agent 0.5-3.5 part, after adding, thin-pass 3-5 bottom sheet, then 130 DEG C-170 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the then mechanical property of test material.
Embodiment
Explain the present invention further below in conjunction with concrete case study on implementation, but case study on implementation does not limit in any form to the present invention.
Contrast case 1
Be 0.1-0.2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 55-60 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then thermal silica 40 parts, hydroxy silicon oil 5 parts, dicumyl peroxide 0.5 part is added, after fully mixing, thin-pass 4 bottom sheet, then temperature be 160 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Contrast case 2
Be 0.1-0.2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 55-60 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then thermal silica 30 parts, hydroxy silicon oil 3 parts, carbon nanotube 5 parts, 2 is added, 5-dimethyl-2,5-bis(t-butylperoxy) hexane 0.8 part, after fully mixing, thin-pass 4 bottom sheet, then temperature be 170 DEG C, pressure be 15MPa vulcanizing press on sulfuration.The mechanical property of test material is as table 1:
Case study on implementation 1
Be 0.1-0.2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 55-60 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then dimethyl diphenylthiuram disulfide 0.6 part, thermal silica 50 parts, hydroxy silicon oil 6 parts, carbon nanotube 3 parts, benzoyl peroxide 3.5 parts is added, after fully mixing, thin-pass 4 bottom sheet, then temperature be 140 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Case study on implementation 2
Be 0.1-0.2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 55-60 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then tetra-benzyl thiram disulfide 0.4 part is added, thermal silica 40 parts, hydroxy silicon oil 5 parts, carbon nanotube 5 parts, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 2.5 parts, after fully mixing, thin-pass 4 bottom sheet, then temperature be 170 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Case study on implementation 3
Be 0.1-0.2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 55-60 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then diethyl diphenyl thiuram disulfide 0.7 part is added, thermal silica 50 parts, hydroxy silicon oil 6 parts, carbon nanotube 5 parts, dicumyl peroxide 2.2 parts, after fully mixing, thin-pass 4 bottom sheet, then temperature be 150 DEG C, pressure be 10MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Case study on implementation 4
Be 2% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 35-40 about ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then methylenediphenyl diamines 0.2 part is added, thermal silica 30 parts, hydroxy silicon oil 4 parts, carbon nanotube 10 parts, 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexane 2.5 parts, after fully mixing, thin-pass 4 bottom sheet, then temperature be 160 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Case study on implementation 5
Be 5% by 100 grams of contents of ethylene, molecular weight is that the silicon rubber of 25-30 ten thousand is put in two roller mills of room temperature, after stablizing bag roller, then dibenzyl amine 0.8 part is added, thermal silica 40 parts, hydroxy silicon oil 5 parts, carbon nanotube 3 parts, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane 3.1 parts, after fully mixing, thin-pass 4 bottom sheet, then temperature be 170 DEG C, pressure be 15MPa vulcanizing press on sulfuration, the mechanical property of test material is as table 1:
Table 1 High tear resistance silicon rubber mechanics properties testing result
Claims (5)
1. a High tear resistance silicon rubber nano-complex, is characterized in that by weight, comprises following composition:
100 parts, silicon rubber, carbon nanotube 3-10 part, thermal silica 30-50 part, hydroxy silicon oil 3-6 part, vulcanizing agent 0.5-3.5 part and interfacial agents 0.2-0.8 part; The molar fraction 0.05%-5% of silicon rubber medium vinyl, number-average molecular weight 300000-1000000; Interfacial agents comprises tetra-benzyl thiram disulfide, dimethyl diphenylthiuram disulfide, diethyl diphenyl thiuram disulfide, dibenzothiazyl disulfide, and methylenediphenyl diamines is or/and dibenzyl amine.
2. a kind of High tear resistance silicon rubber nano-complex according to claim 1, is characterized in that:
The vinyl molar fraction of described silicon rubber is 0.1-0.3%, and molecular weight is 400000-60000.
3. a kind of High tear resistance silicon rubber nano-complex according to claim 1, is characterized in that:
Described interfacial agents is tetra-benzyl thiram disulfide.
4. a kind of High tear resistance silicon rubber nano-complex according to claim 1, is characterized in that:
Described peroxide comprises benzoyl peroxide, 2,5-dimethyl-2,5-bis-(benzoyl peroxide) hexanes or/and dicumyl peroxide.
5. a kind of High tear resistance silicon rubber nano-complex according to any one of claim 1-4, it is characterized in that, preparation technology is:
By weight, 100 parts of silicon rubber are placed in the mill of room temperature, after stablizing bag roller, add interfacial agents 0.2-0.8 part, carbon nanotube 3-10 part, thermal silica 30-50 part, hydroxy silicon oil 3-6 part, vulcanizing agent 0.5-3.5 part, after adding, thin-pass 3-5 bottom sheet, then 130 DEG C-170 DEG C, pressure be 15MPa vulcanizing press on sulfuration.
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| CN107298859A (en) * | 2017-02-28 | 2017-10-27 | 苏州柔触机器人科技有限公司 | A kind of flexible material |
| CN108624052A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | A method of improving phenyl siloxane rubber mechanical property |
| CN108624051A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | A kind of hydroxy-terminated polysiloxane is carbon nano-tube modified-phenyl siloxane rubber composite material and preparation method |
| CN108624058A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | A method of improving methyl vinyl silicone rubber mechanical property |
| CN108624059A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | A method of improving methyl vinyl silicone rubber thermal stability |
| CN108624050A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | A method of improving phenyl siloxane rubber thermal stability |
| CN108623846A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | Silicon-carbon composite nano tube and its preparation method and application |
| CN110894363A (en) * | 2019-12-09 | 2020-03-20 | 株洲时代新材料科技股份有限公司 | Tear-resistant organic silicon foam material and preparation method thereof |
| CN111875967A (en) * | 2020-06-29 | 2020-11-03 | 安徽浩天新型材料有限公司 | Silicon rubber cable protection pipe |
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| CN107298859A (en) * | 2017-02-28 | 2017-10-27 | 苏州柔触机器人科技有限公司 | A kind of flexible material |
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| CN110894363A (en) * | 2019-12-09 | 2020-03-20 | 株洲时代新材料科技股份有限公司 | Tear-resistant organic silicon foam material and preparation method thereof |
| CN111875967A (en) * | 2020-06-29 | 2020-11-03 | 安徽浩天新型材料有限公司 | Silicon rubber cable protection pipe |
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