CN1970635A - Heat cured silicon rubber nano composite material and preparation process thereof - Google Patents
Heat cured silicon rubber nano composite material and preparation process thereof Download PDFInfo
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- CN1970635A CN1970635A CN 200610118194 CN200610118194A CN1970635A CN 1970635 A CN1970635 A CN 1970635A CN 200610118194 CN200610118194 CN 200610118194 CN 200610118194 A CN200610118194 A CN 200610118194A CN 1970635 A CN1970635 A CN 1970635A
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- organo montmorillonite
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Abstract
The invention discloses a heat sulfurizing typed silicon rubber nanometer composite material and making method, which comprises the following parts: 50% raw rubber of methyl vinyl silicon rubber, 0.5-0.8% 2, 4-ditert-butyl peroxy hexane and 49.2-49.5% organic montmorillonite masterbatch. The invention enlarges chemical reaction contact area and acitivty, which improves stretching strength and fracture extending rate obviously.
Description
Technical field
The present invention relates to heat cured silicon rubber nano composite material and preparation method thereof, relate in particular to heat cured silicon rubber nano composite material that adopts organo montmorillonite master batch calendering process and preparation method thereof.
Background technology
Silicon rubber is the macromolecular material that a kind of molecular chain has inorganic and organic character concurrently, and its molecular backbone chain alternately is made up of Siliciumatom and Sauerstoffatom, and siloxane bond is more much bigger in conjunction with bond energy than general carbon-to-carbon, and this makes silicon rubber have very high thermostability.
Hot-vulcanized silicone rubber is a most important class in the silicone rubber products, and methyl vinyl silicone rubber is wherein topmost kind, is commonly called as high-temp glue.Methyl vinyl silicone rubber (rubber) is the jelly of colourless, odorless, nontoxic, no mechanical impurity, it is mixing together that rubber adds auxiliary agents such as suitable strengthening agent, constitution controller, vulcanizing agent on demand, and various goods are made in heat up then compression molding or extrusion moulding.Its goods have excellent electric insulation, and anti-electric-arc, corona, electrical spark ability are strong, and waterproof, protection against the tide, anti-impact force, shock resistance are good, have the physiology inertia, performances such as ventilation property.Be mainly used in departments such as aviation, instrument, electronic apparatus, navigation, metallurgy, machinery, automobile, health care, can do sealing-ring, pad, pipe, the cable of different shape, also can make the releasing agent of human body organ, blood vessel, air-permeable envelope and rubber mold, precision casting etc.
Silicon rubber has good heat-proof aging and weather-proof aging, and is very stable to the effect of ultraviolet and ozone.The silica chain is configuration in the shape of a spiral, and the snappiness of molecular chain is big, and a little less than the molecule interchain interaction force, these constitutional featuress make its cross-linked rubber softness and high resilience, but physical and mechanical properties is relatively poor.
The method that now more successfully prepares high-strength silicone rubber has: 1. adopt the white carbon black of handling, for example with 4 of hexamethyldisilazane processing
#Thermal silica, promptly high anti-tear white carbon black (or claiming high-reinforcement white carbon black), tear strength can reach 40～50kN/m.2. in vinylsiloxane rubber, add high-vinyl-content and polysiloxane that relative molecular mass is lower (being commonly called as C glue), with 4
#White carbon black is that strengthening agent, siloxanes are constitution controller, tear strength can be brought up to 4050kN/m.
Compare with organic rubber, though the physical strength at normal temperatures of the silicon rubber after the reinforcement is still not as natural rubber, styrene-butadiene rubber(SBR) etc., owing to its good heat resistance, so at high temperature can show good mechanical property.Though above method can effectively improve the intensity of silicon rubber owing to the mixing difficulty of thermal silica, fly upward big, easily structurizing, cause processed complex, and high anti-tear white carbon black prices are rather stiff, increased cost greatly.In recent years, nano composite polymer-montmorillonoid material has become the focus of current polymer materials Application and Development because be better than general polymeric material in preparation, structure, performance and application facet.The polynite of using in this material, preparation technology is simple, with low cost, but must adopt physics or chemical graft process to make polynite be the nano-lamellar structure state is dispersed in the polymkeric substance, and in the course of processing, be difficult to make polynite to reach above-mentioned requirements as solid-state heat vulcanized silicone rubber, therefore become a calendering process bottleneck of its widespread use in this system.
Summary of the invention
The calendering process problem that the present invention need solve is to disclose a kind of heat cured silicon rubber nano composite material and preparation method thereof, to overcome the defective of current material.
The component of heat cured silicon rubber nano composite material of the present invention and weight part are:
50 parts of methyl vinyl silicon kautschuks
2,0.5～0.8 part of 4-di-tert-butyl peroxide hexane
49.2～49.5 parts of organo montmorillonite master batchs
Said methyl vinyl silicon kautschuk can adopt business-like product, as the high temperature vulcanizable silicone series product of Huitian New Material in Chemcal Engineering Co., Ltd., Shanghai's production;
Said 2,4-di-tert-butyl peroxide hexane can adopt business-like product, the high temperature vulcanizable silicone series product of producing as Huitian New Material in Chemcal Engineering Co., Ltd., Shanghai;
In the said organo montmorillonite master batch, the weight content of organo montmorillonite is 30～50%;
The preparation method of said organo montmorillonite master batch comprises the steps:
At first 50～70 gram methyl vinyl silicon kautschuks are dissolved in and make the lower solution of viscosity in 100 milliliters of toluene solutions;
Then the organo montmorillonite of 30～50 grams is slowly poured in the above-mentioned solution, stirred 1～3 hour, obtain containing the silicone rubber solution of nano organic montmorillonite;
At last this silicone rubber solution is at room temperature hung 12～30 hours, and put into 40～60 ℃ of dryings of loft drier 8～12 hours, the toluene solvant in the silicon rubber is removed fully, make 30～50% organo montmorillonite master batch;
Said organo montmorillonite is the nonmetal stratiform silicate minerals of a class through the organic intercalation agent modification, main mineralogical composition is the layered silicate that contains 90～95% polynites, one deck silica is octahedra to be formed its unit cell by carrying secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two; Said intercalator is C
12～C
18Terminal hydroxy group quaternary ammonium salt or hold amino quaternary ammonium salt, for example: dihydroxyl trimethyldodecane base brometo de amonio, montmorillonite modified can adopt business-like product, and the trade mark of producing as Zhejiang Feng Hong clay company limited is the product of DK2.
Heat cured silicon rubber nano composite material preparation method of the present invention comprises the steps:
Proportionally, methyl vinyl silicon kautschuk and said organo montmorillonite master batch is mixing in mill, and temperature is 30～50 ℃, and the time is 0.2～0.5 hour;
Proportionally add 2,4-di-tert-butyl peroxide hexane, slice after mixing 10～30 minutes;
Above-mentioned film is vulcanized on vulcanizing press, and cure conditions is 165～175 ℃ * 5～10 minutes, can make heat cured silicon rubber nano composite material of the present invention.
Heat cured silicon rubber nano composite material of the present invention, because the polynite in the organo montmorillonite master batch is dispersed in the polymeric matrix with the nanometer lamella, the nanometer lamella can show excellent properties such as small-size effect, interfacial effect and quantum tunneling effect, increases the contact surface and the activity of its chemical reaction greatly.Therefore in the present invention, the tensile strength of 20% organic montmorillonite/heat vulcanization type silicon rubber nano composite material is compared with the silicon rubber of direct adding 20% organo montmorillonite with elongation at break, has had largely to improve; And its tensile strength approaches to add the reinforcing effect of the silicon rubber of 20% gas-phase silica, and mechanical property such as elongation at break have also had largely and improve.
Embodiment
Embodiment 1
At first 70 gram methyl vinyl silicone rubbers (rubber) are dissolved in and make the lower solution of viscosity in 100 milliliters of toluene solutions; Then 30 gram organo montmorillonites are poured in the above-mentioned solution, stirred 1 hour, obtain containing the silicone rubber solution of nano organic montmorillonite; At last this silicone rubber solution is at room temperature hung 30 hours, and put into 40 ℃ of dryings of loft drier 12 hours, the toluene solvant in the silicon rubber is removed fully, make 30% organo montmorillonite master batch.
With 50 gram methyl vinyl silicone rubbers (rubber) and 50 restrain 30% organo montmorillonite master batch in mill 30 ℃ mixing 0.5 hour, add 0.5 gram 2 then, 4-di-tert-butyl peroxide hexane, slice after mixing 20 minutes, again above-mentioned film is vulcanized on vulcanizing press, cure conditions is 165 ℃ * 10 minutes, promptly obtains 15% organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 2
At first 60 gram methyl vinyl silicone rubbers (rubber) are dissolved in and make the lower solution of viscosity in 90 milliliters of toluene solutions; Then 40 gram organo montmorillonites are slowly poured in the above-mentioned solution, stirred 2 hours, obtain containing the silicone rubber solution of nano organic montmorillonite; At last this silicone rubber solution is at room temperature hung 24 hours, and put into 50 ℃ of dryings of loft drier 10 hours, the toluene solvant in the silicon rubber is removed fully, make 40% organo montmorillonite master batch.
With 50 gram methyl vinyl silicone rubbers (rubber) and 50 restrain 40% organo montmorillonite master batch in mill 40 ℃ mixing 0.3 hour, add 0.6 gram 2 then, 4-di-tert-butyl peroxide hexane, slice after mixing 30 minutes, above-mentioned film is vulcanized on vulcanizing press, cure conditions is 170 ℃ * 8 minutes, promptly obtains 20% organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Embodiment 3
At first 50 gram methyl vinyl silicone rubbers (rubber) are dissolved in and make the lower solution of viscosity in 80 milliliters of toluene solutions; Then 50 gram organo montmorillonites are slowly poured in the above-mentioned solution, stirred 3 hours, obtain containing the silicone rubber solution of nano organic montmorillonite; At last this silicone rubber solution was at room temperature hung 12 hours, put into 60 ℃ of dryings of loft drier then 8 hours, the toluene solvant in the silicon rubber is removed fully, make 50% organo montmorillonite master batch.
With 50 gram methyl vinyl silicone rubbers (rubber) and 50 restrain 50% organo montmorillonite master batch in mill 50 ℃ mixing 0.2 hour, 0.7 restrain 2 then, 4-di-tert-butyl peroxide hexane, mixing 10 minutes slices, above-mentioned film is vulcanized on vulcanizing press, cure conditions is 175 ℃ * 5 minutes, promptly obtains 25% organic montmorillonite/heat vulcanization type silicon rubber nano composite material of the present invention.This nano composite material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 1
With 85 gram methyl vinyl silicone rubbers (rubber) and 15 restrain organo montmorillonites in mill 30 ℃ mixing 0.5 hour, add 0.5 gram 2 then, 4-di-tert-butyl peroxide hexane, mixing 20 minutes, slice is vulcanized above-mentioned film on vulcanizing press, cure conditions is 175 ℃ * 5 minutes, promptly obtains 15% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 2
With 80 gram methyl vinyl silicone rubbers (rubber) and 20 restrain organo montmorillonites in mill 40 ℃ mixing 0.4 hour, add 0.6 gram 2 then, 4-di-tert-butyl peroxide hexane, mixing 20 minutes, slice is vulcanized above-mentioned film on vulcanizing press, cure conditions is 175 ℃ * 5 minutes, promptly obtains 20% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 3
With 75 gram methyl vinyl silicone rubbers (rubber) and 25 restrain organo montmorillonites in mill 45 ℃ mixing 0.3 hour, add 0.7 gram 2 then, 4-di-tert-butyl peroxide hexane, mixing 20 minutes, slice is vulcanized above-mentioned film on vulcanizing press, cure conditions is 175 ℃ * 5 minutes, promptly obtains 25% organic montmorillonite/heat vulcanization type silicon rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Comparative Examples 4
With 80 gram methyl vinyl silicone rubbers (rubber) and 20 restrain gas-phase silicas in mill 50 ℃ mixing 0.2 hour, add 0.8 gram 2 then, 4-di-tert-butyl peroxide hexane, mixing 20 minutes, slice is vulcanized above-mentioned film on vulcanizing press, cure conditions is 175 ℃ * 5 minutes, promptly obtains 20% gas-phase silica/heat vulcanized silicone rubber matrix material.This matrix material is made dumbbell-shaped specimen, and carry out stretching experiment by GB/T1701-2001, gained tensile strength and elongation at break see Table 1.
Table 1
| Embodiment | Tensile strength (MPa) | Elongation at break (%) |
| Comparative Examples 1 | 0.51 | 240 |
| Comparative Examples 2 | 0.57 | 260 |
| Comparative Examples 3 | 0.54 | 220 |
| Comparative Examples 4 | 1.44 | 380 |
| Embodiment 1 | 0.89 | 390 |
| Embodiment 2 | 1.41 | 490 |
| Embodiment 3 | 1.21 | 470 |
Claims (4)
1. a heat cured silicon rubber nano composite material is characterized in that, component and weight part are:
50 parts of methyl vinyl silicon kautschuks
2,0.5～0.8 part of 4-di-tert-butyl peroxide hexane
49.2～49.5 parts of organo montmorillonite master batchs.
In the said organo montmorillonite master batch, the weight content of organo montmorillonite is 30～50%.
2. material according to claim 1 is characterized in that the preparation method of said organo montmorillonite master batch comprises the steps:
At first 50～70 gram methyl vinyl silicon kautschuks are dissolved in and make the lower solution of viscosity in 100 milliliters of toluene solutions;
Then the organo montmorillonite of 30～50 grams is slowly poured in the above-mentioned solution, stirred 1～3 hour, obtain containing the silicone rubber solution of nano organic montmorillonite;
At last this silicone rubber solution is at room temperature hung 12～30 hours, and put into 40～60 ℃ of dryings of loft drier 8～12 hours, the toluene solvant in the silicon rubber is removed fully, make 30～50% organo montmorillonite master batch.
3. material according to claim 2 is characterized in that, said organo montmorillonite is the nonmetal stratiform silicate minerals of a class through the organic intercalation agent modification; Said intercalator is C12～C18 terminal hydroxy group quaternary ammonium salt or holds amino quaternary ammonium salt.
4. according to claim 1,2 or 3 described preparation methods, it is characterized in that, comprise the steps:
Proportionally, methyl vinyl silicon kautschuk and said organo montmorillonite master batch is mixing in mill, and temperature is 30～50 ℃, and the time is 0.2～0.5 hour;
Proportionally add 2,4-di-tert-butyl peroxide hexane, slice after mixing 10～30 minutes;
Above-mentioned film is vulcanized on vulcanizing press, and cure conditions is 165～175 ℃ * 5～10 minutes, can make heat cured silicon rubber nano composite material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831084A (en) * | 2010-06-03 | 2010-09-15 | 天津大学 | Organically-modified MMT and cross-linking method for high-temperature silicon disulfide rubber |
| CN102911414A (en) * | 2012-10-17 | 2013-02-06 | 青岛佳之源轮胎维修有限公司 | Low-temperature vulcanized masterbatch and preparation method thereof |
| CN103159990A (en) * | 2011-12-08 | 2013-06-19 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN103275495A (en) * | 2013-05-27 | 2013-09-04 | 上海工程技术大学 | Composite flame-retardant silicone rubber material with high thermal stability and preparation method thereof |
| CN104774469A (en) * | 2015-03-16 | 2015-07-15 | 芜湖荣基密封系统有限公司 | Molybdenum disulfide (MoS2) doped wear-resistant silicone rubber cement with high seepage resistant performance for preparing ultrathin sealing rubber layers and preparation method thereof |
| CN104987727A (en) * | 2015-07-20 | 2015-10-21 | 上海工程技术大学 | Preparation method for silicon rubber containing organically modified montmorillonite |
| CN106046791A (en) * | 2016-07-05 | 2016-10-26 | 苏州科淼新材料有限公司 | Nanometer rubber and method for preparing same |
| CN112111155A (en) * | 2019-06-19 | 2020-12-22 | 中国科学院化学研究所 | Blended polymer material of polyalkylmethacrylate and silicone rubber, preparation method and application thereof |
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2006
- 2006-11-10 CN CNB2006101181940A patent/CN100480332C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831084A (en) * | 2010-06-03 | 2010-09-15 | 天津大学 | Organically-modified MMT and cross-linking method for high-temperature silicon disulfide rubber |
| CN103159990A (en) * | 2011-12-08 | 2013-06-19 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN103159990B (en) * | 2011-12-08 | 2014-12-31 | 中国石油化工股份有限公司 | Master batch and preparation method thereof, and vulcanized rubber and applications thereof |
| CN102911414A (en) * | 2012-10-17 | 2013-02-06 | 青岛佳之源轮胎维修有限公司 | Low-temperature vulcanized masterbatch and preparation method thereof |
| CN102911414B (en) * | 2012-10-17 | 2015-01-14 | 青岛佳之源轮胎维修有限公司 | Low-temperature vulcanized masterbatch and preparation method thereof |
| CN103275495A (en) * | 2013-05-27 | 2013-09-04 | 上海工程技术大学 | Composite flame-retardant silicone rubber material with high thermal stability and preparation method thereof |
| CN104774469A (en) * | 2015-03-16 | 2015-07-15 | 芜湖荣基密封系统有限公司 | Molybdenum disulfide (MoS2) doped wear-resistant silicone rubber cement with high seepage resistant performance for preparing ultrathin sealing rubber layers and preparation method thereof |
| CN104987727A (en) * | 2015-07-20 | 2015-10-21 | 上海工程技术大学 | Preparation method for silicon rubber containing organically modified montmorillonite |
| CN104987727B (en) * | 2015-07-20 | 2017-09-26 | 上海工程技术大学 | A kind of preparation method of the silicon rubber containing organic modification montmonrillonite |
| CN106046791A (en) * | 2016-07-05 | 2016-10-26 | 苏州科淼新材料有限公司 | Nanometer rubber and method for preparing same |
| CN112111155A (en) * | 2019-06-19 | 2020-12-22 | 中国科学院化学研究所 | Blended polymer material of polyalkylmethacrylate and silicone rubber, preparation method and application thereof |
| CN112111155B (en) * | 2019-06-19 | 2022-04-01 | 中国科学院化学研究所 | Blended polymer material of polyalkylmethacrylate and silicone rubber, preparation method and application thereof |
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| CN100480332C (en) | 2009-04-22 |
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