CN1063202C - Sandwiched Silicon rubber/montmorillonoid composite material and its preparing method - Google Patents
Sandwiched Silicon rubber/montmorillonoid composite material and its preparing method Download PDFInfo
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- CN1063202C CN1063202C CN97103917A CN97103917A CN1063202C CN 1063202 C CN1063202 C CN 1063202C CN 97103917 A CN97103917 A CN 97103917A CN 97103917 A CN97103917 A CN 97103917A CN 1063202 C CN1063202 C CN 1063202C
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- polynite
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Abstract
The present invention relates to a silicon rubber / montmorillonite intercalation composite material and a preparation method thereof. After montmorillonite is treated by a cation exchange reaction, the montmorillonite is uniformly dispersed in raw rubber of silicon rubber, and is formed by solidification by adding crosslinking agents and initiators. The mechanical property, the heat resistance and the solvent resistance of the composite material are obviously enhanced. The cost is obviously reduced.
Description
The present invention relates to a kind of silicon rubber composite material that uses inorganic batch, specially refer to a kind of class montmorillonite filled silicon rubber and the intercalation composite material that forms.
At present, industrial silicon rubber mainly is to come reinforcement with fumed silica (white carbon black), but this silicon-dioxide price is expensive, and because its particle diameter is very little by (5～20nm), easily gathering is agglomerating, is difficult for being dispersed in the rubber, also is inhaled into human body during operation easily, very big to the healthy influence of operator, easily cause " silicosis ".In order to overcome white carbon black dust in the existing mode to the healthy influence of operator and the unfavorable factor of the white carbon black selling at exorbitant prices of vapor phase process, the present invention adopts low-cost polynite to strengthen silicon rubber, utilize silicon rubber molecular chain intercalation to enter the ultrafine particulate that makes polynite be cleaved into nearly hundred nanometer scale between the silicate lamella of polynite and be evenly dispersed in the silicon rubber matrix, the reinforced rubber that obtains at last has perfect performance.Its application prospect is very wide.
The patent that had not only related to silicon rubber but also related to polynite has the United States Patent (USP) US5357016 and the US4983377 on January 8th, 1991 on October 18th, 1994, and the flat 4-19269 of JP, the clear 61-271030 of JP on December 1st, 1986, the clear 59-71340 of JP on April 23rd, 1984 and the clear 61-113646 of JP on May 31st, 1986 in Japanese Patent on March 30th, 1992.Patent US5357016 is the building-up reactions of polysiloxane, and polynite is as catalyzer in this reaction, mainly is to utilize the ion on polynite surface to come the polyreaction of catalyze siloxane, does not relate to class montmorillonite filled silicon rubber and the matrix material that forms.Polynite is to be used for a kind of molecule is scattered in the silicon rubber among the patent US4983377, and this dispersion process is also used solvent, solvent evaporates in the compound system, the residuum moulding, rather than silicon rubber/montmorillonite composite adds the solidifying agent curing molding in this patent.The flat 4-19269 of patent JP is a kind of gelling system that silicone oil and polynite, water etc. form, and does not add the solidifying agent curing molding and forms silicon rubber.The clear 61-271030 of patent JP also is a kind of jelly that silicone oil and polynite etc. form, and does not add the solidifying agent curing molding and forms silicon rubber.The clear 59-71340 of patent JP mainly is the modification of polynite, and it does not use protonating agent.The clear 61-113646 of patent JP is a kind of jelly that silicone oil and polynite, water etc. form, and does not add the solidifying agent curing molding.
Novel intercalation composite material that the invention provides the class montmorillonite filled silicon rubber of a kind of usefulness and form and preparation method thereof shows that through the Searches of Patent Literature the present invention does not have the report of identical content at home and abroad on the publication.
The component of silicon rubber of the present invention/montmorillonite laminated compound material raw material and consumption following (weight part):
Raw-silastic continuously 100
Polynite 0.5～50
Cationite 0.1～15
Protonating agent 0～20
Dispersion medium 100～1100
Solidifying agent 0.1～5
Initiator 0.1～1.5
The raw-silastic continuously that the present invention was suitable for is polydimethylsiloxane, poly-ethylene methacrylic radical siloxane, PSI etc.
The used polynite of the present invention is a kind of nonmetal stratiform silicate minerals, and its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.The montmorillonite layer internal surface has negative charge, interlayer cation Na
+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, after cationic exchange, can make polysiloxane macromonomer be inserted into interlayer.Polynite should have cationic exchange total volume (CEC) 50～200meq/100g, is preferably 70～110 meq/100g.When exchange capacity CEC greater than 200 meq/100g, higher interlayer Coulomb's force makes polynite be difficult for being dispersed in the polymeric matrix; When exchange capacity is lower than 50meq/100g, polynite can not interact with polysiloxane macromonomer effectively, thereby is not enough to guarantee the consistency of polynite and polymeric matrix, makes polynite be difficult for being dispersed in the polymeric matrix equally.
The used polynite of the present invention preferably is crushed to suitable particle diameter, with ball mill, vibration mill, jet mill etc. polynite is ground into desirable particle size then.General particle diameter should be at 50～100 μ m.
The polynite consumption is 0.5～50 part (weight part is with respect to 100 parts of raw-silastic continuouslies) in the present invention.When consumption is lower than 0.5 part, polynite is not enough to produce enough enhancements; When consumption surpasses 50 parts, matrix material utmost point thickness can not flowing forming.In the present invention, the optimum amount scope of polynite is 2.5～25 parts.
Cationite of the present invention is a polyamines, can be diamines, triamine or tetramine, as cetyl trimethylammonium bromide, 6-aminocaprolc acid, trolamine etc.When adopting tetramine, do not need other protonation agent; And when adopting diamines or triamine, need other protonation agent.
The protonating agent that the present invention was suitable for can be sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid etc.
The effect of the dispersion medium that the present invention is used is to promote the dispersion of montmorillonite particle and the carrying out of cation exchange reaction, can be water, alcohols, N, dinethylformamide etc.
Solidifying agent of the present invention participates in the curing reaction of silicon rubber, can be the alkyl silane of multiple functional radical, the organoalkoxysilane of multiple functional radical etc., as tetraethoxy.
Initiator of the present invention is a dibutyl tin laurate.
Silicon rubber of the present invention/montmorillonite laminated compound material preparation method is undertaken by following step:
It at first is the cation exchange reaction of polynite.With the cationic exchange total volume is 0.5～50 part of the polynite of 50～200 meq/100g, and high-speed stirring in the presence of 100～800 parts dispersion medium forms stable suspersion system A.0.1～15 part of cationite is dissolved in 30～250 parts of dispersion medium, adds 0～20 part of protonating agent, form solution B.Suspension system A is heated to 70～90 ℃, solution B is dripped in A, 70～90 ℃ through 0.5～2 hour, make polynite colloidal sol, with this colloidal sol suction filtration, washing, vacuum-drying, pulverize and to obtain the polynite powder.
Be with silicon rubber and polynite powder mixes and curing then.0.5～50 part of above-mentioned polynite through cation exchange reaction is scattered in 100 parts of raw-silastic continuouslies with machine,massing, stir and add 0.1～5 part of solidifying agent, 0.1～1.5 part of initiator after 1～8 hour, stir, pour in the mould, placed 10～24 hours down at 15～130 ℃, promptly get product.
Silicon rubber/montmorillonite laminated compound material of the present invention makes polynite have very big interfacial area, inorganic disperse phase and silicone rubber based body interface have the ideal adhesiveproperties, improve shock strength, can eliminate inorganics and polymeric matrix two material thermal expansivity mismatch problems.
Silicon rubber/montmorillonite laminated compound material of the present invention enters in the middle of the montmorillonite layer part polysiloxane macromonomer, has strengthened inorganics and polymeric matrix interphase interaction, and the mechanical property of matrix material is greatly improved.Reactive terminal inactivation when polynite simultaneously can make the siloxane main chain degraded; Polynite and silicon rubber interphase interaction increase the physical crosslinking of matrix material, chemically crosslinked point, and higher cross-linking density can suppress the button of separating of siloxane main chain and degrade.These all impel the thermotolerance of matrix material that further raising is arranged, and can reach 433 ℃.The adding of polynite has also improved the solvent resistance of matrix material simultaneously.
Silicon rubber/montmorillonite laminated compound material of the present invention overcome that white carbon black in the traditional way is difficult for disperseing and dust to the shortcoming of operator actual bodily harm.The preparation manipulation of matrix material is simple, convenient, safety, and the polynite price is starkly lower than the white carbon black of vapor phase process, and the matrix material cost is obviously reduced.
Embodiment 1
With the cationic exchange total volume is the polynite 2.5g of 100meq/100g, adds water 100ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.1.6g cetyl trimethylammonium bromide is dissolved in the 30ml water, gets solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g polydimethylsiloxane with machine,massing, stirred 3 hours, add 1.25g tetraethoxy and 0.3g dibutyl tin laurate, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get matrix material.Its performance sees Table 1.
Embodiment 2
With the cationic exchange total volume is the polynite 5g of 100meq/100g, adds water 200ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.3.2g cetyl trimethylammonium bromide is dissolved in the 60ml water, gets solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g polydimethylsiloxane with machine,massing, stirred 3 hours, add positive silicic acid ethanol of 1.25g and 0.3g dibutyl tin laurate, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get matrix material.Its performance sees Table 1.
Embodiment 3
With the cationic exchange total volume is the polynite 7.5g of 80meq/100g, adds water 300ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.4.8g cetyl trimethylammonium bromide is dissolved in the 90ml water, gets solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g polydimethylsiloxane with machine,massing, stirred 3 hours, add 1.25g tetraethoxy and 0.3g dibutyl tin laurate, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get matrix material.Its performance sees Table 1.
Embodiment 4
With the cationic exchange total volume is the polynite 10g of 100meq/100g, adds water 400ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.6.4g cetyl trimethylammonium bromide is dissolved in the 120ml water, gets solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g polydimethylsiloxane with machine,massing, stirred 3 hours, add people 1.25g tetraethoxy and 0.3g dibutyl tin laurate, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get matrix material.Its performance sees Table 1.
Embodiment 5
With the cationic exchange total volume is the polynite 20g of 100 meq/100g, adds water 800ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.12.8g cetyl trimethylammonium bromide is dissolved in the 240ml water, gets solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being bromide anion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g polydimethylsiloxane with machine,massing, stirred 3 hours, add 1.25g tetraethoxy and 0.3g dibutyl tin laurate, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get matrix material.Its performance sees Table 1.
Embodiment 6 (Comparative Examples)
Add 1.25g tetraethoxy and 0.3g dibutyl tin laurate in the 100g polydimethylsiloxane, stir, pour in the mould, placed at least 12 hours under 15～30 ℃, promptly get Comparative Examples.Its performance sees Table 1.
Embodiment 7
With the cationic exchange total volume is the polynite 25g of 100meq/100g, adds water 600ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.13.5g6-hexosamine is dissolved in the 240ml water, drips concentration and is 37% hydrochloric acid 8ml and get solution B.Suspending liquid A is heated to 80 ℃, drips solution B, and temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, detect filtrate to there not being chlorion with 0.2% silver nitrate solution, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the poly-ethylene methacrylic radical siloxane of 100g with machine,massing, stirred 3 hours, add 4.5g tetraethoxy and 1.3g dibutyl tin laurate, stir, in the mould of falling people, placed 10 hours down, promptly get matrix material for 110～120 ℃.
Embodiment 8
With the cationic exchange total volume is the polynite 25g of 100meq/100g, adds water 600ml, and after waiting to be uniformly dispersed, high-speed stirring 20min gets suspending liquid A.6.5g trolamine is dissolved in the 150ml water, drips concentration and is 30% sulfuric acid 17ml and get solution B.Suspending liquid A is heated to 80 ℃.Drip solution B, temperature maintenance is incubated 1 hour at 80 ℃, naturally cools to 20～25 ℃, suction filtration, and wash with water repeatedly, be dried to constant weight in the vacuum, be milled to powder.This powder is scattered in the 100g PSI with machine,massing, stirred 3 hours, add positive silicic acid ethanol of 3.0g and 0.8g dibutyl tin laurate, stir, pour in the mould, placed 10 hours down, promptly get matrix material for 110～120 ℃.Table 1
Claims (4)
1. a silicon rubber/montmorillonite laminated compound material comprises silicon rubber and polynite, the feed composition and the content that it is characterized in that described matrix material are as follows: (weight part) raw-silastic continuously 100 polynite 0.5～50 cationite, 0.1～15 protonating agent sulfuric acid or hydrochloric acid 0～20 dispersion medium water 100～1100 solidifying agent tetraethoxys 0.1～5 initiator dibutyl tin laurate 0.1～1.5 described raw-silastic continuously are polydimethylsiloxanes, poly-ethylene methacrylic radical siloxane or PSI, described polynite particle diameter is 50-100 μ m, its cationic exchange total volume is 50～200meq/100g, and described cationite is a cetyl trimethylammonium bromide, 6 one hexosamines or trolamine.
2. a kind of silicon rubber/montmorillonite laminated compound material according to claim 1 is characterized in that described polynite content is 2.5～25 parts.
3. a kind of silicon rubber/montmorillonite laminated compound material according to claim 1, the cationic exchange total volume that it is characterized in that described polynite is 70～110meq/100g.
4. the preparation method of a silicon rubber/montmorillonite laminated compound material is characterized in that being undertaken by following step:
With the cationic exchange total volume is polynite 0.5-50 part of 50～200 meq/100 g, high-speed stirring in the presence of the dispersion medium of 100-800 part forms stable suspersion system A, and 0.1～15 part of cationite is dissolved in 30～250 parts of dispersion medium, add 0～20 part of protonating agent, form solution B, suspension system A is heated to 70～90 ℃, solution B is dripped in A, at 70～90 ℃ through 0.5～2 hour, make polynite colloidal sol. through washing, drying, be broken into the polynite powder
Above-mentioned polynite powder through cation exchange reaction is scattered in 100 parts of raw-silastic continuouslies for 0.5～50 part, stir and add 0.1～5 part of solidifying agent, 0.1～1.5 part of initiator after 1～8 hour, pour in the mould, placed 10～24 hours down, promptly get product for 15～130 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295279C (en) * | 2005-08-16 | 2007-01-17 | 上海工程技术大学 | Add-on type liquid silicon rubber/organic montmorillonite nanometer composite material and its preparation method |
| CN107412873A (en) * | 2017-05-02 | 2017-12-01 | 北京化工大学 | A kind of high anti-tear antibiotic property breast prosthesis impervious barrier material preparation method |
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| JP4279052B2 (en) * | 2003-05-23 | 2009-06-17 | 新道繊維工業株式会社 | Emulsion composition for silicone rubber. |
| CN107227141A (en) * | 2017-06-28 | 2017-10-03 | 常州市万昌化工有限公司 | A kind of weather-proof crack resistence type fluid sealant |
| CN108929543A (en) * | 2018-08-27 | 2018-12-04 | 南京师范大学 | Silicon rubber/carrying nano silver ester/modified montmorillonite nano antimicrobial composite material and preparation method thereof |
| CN113388253B (en) * | 2021-06-24 | 2022-06-28 | 北京航空航天大学 | Preparation method of abalone shell-imitated montmorillonite-polydimethylsiloxane nanocomposite |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61113646A (en) * | 1984-11-08 | 1986-05-31 | Shiseido Co Ltd | Gel composition containing silicone oil |
| JPS61271030A (en) * | 1985-05-28 | 1986-12-01 | Shiseido Co Ltd | Oily gel composition |
| JPS649269A (en) * | 1987-06-30 | 1989-01-12 | Sumitomo Chemical Co | Preparation of copper phthalocyanine pigment |
| US4983377A (en) * | 1989-10-31 | 1991-01-08 | The Procter & Gamble Company | Silicone hairspray compositions |
-
1997
- 1997-04-16 CN CN97103917A patent/CN1063202C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61113646A (en) * | 1984-11-08 | 1986-05-31 | Shiseido Co Ltd | Gel composition containing silicone oil |
| JPS61271030A (en) * | 1985-05-28 | 1986-12-01 | Shiseido Co Ltd | Oily gel composition |
| JPS649269A (en) * | 1987-06-30 | 1989-01-12 | Sumitomo Chemical Co | Preparation of copper phthalocyanine pigment |
| US4983377A (en) * | 1989-10-31 | 1991-01-08 | The Procter & Gamble Company | Silicone hairspray compositions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1295279C (en) * | 2005-08-16 | 2007-01-17 | 上海工程技术大学 | Add-on type liquid silicon rubber/organic montmorillonite nanometer composite material and its preparation method |
| CN107412873A (en) * | 2017-05-02 | 2017-12-01 | 北京化工大学 | A kind of high anti-tear antibiotic property breast prosthesis impervious barrier material preparation method |
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| CN1163288A (en) | 1997-10-29 |
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