CN102516770A - Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof - Google Patents
Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an environmentally-friendly flame-retardant silicone rubber sponge and a preparation method of the environmentally-friendly flame-retardant silicone rubber sponge. The composition comprises the following components: (A) 100 parts by weight of organic polysiloxane with average molecular formula of R4-2nSiOn, wherein R is phenyl unsubstituted or substituted by methyl, vinyl, phenyl or trifluoropropyl and the like, and can be the same or different; (B) 5-50 parts by weight of organic sulfonyl hydrazide foaming agent and 0.5-20 parts by weight of inorganic foaming agent sodium bicarbonate; (C) 0.1-5 parts by weight of foaming aid alum 2KAl(SO4)2.10H2O; (D) 1-300 parts by weight of reinforcing silicon dioxide; (E) a proper amount of vulcanizing agent for vulcanizing and shaping the A component; and (F) 10-100 parts by weight of environmentally-friendly flame retardant. The environmentally-friendly silicone rubber sponge produced by the preparation method has the advantages that: 1. the surface is smooth and level, the pore diameter is uniform, and the surface skinning thickness is moderate and uniform; 2. the hardness (measured by sponge hardometer) of the foamed sponge is 15-40, the tensile strength is not less than 6kg/cm<2>, and 25% compression load is 0.3-0.8kg/cm; and 3. according to the American UL94 and CSA C22.2 related test standards, the level of the foamed sponge flame retardant achieves V0 level.
Description
One, technical field
The present invention relates to a kind of environmental protection flame retardant silicon rubber foam and preparation method thereof, it belongs to the rubber plastic class.
Two, background technology
Silicon rubber foam is used for the occasion of requirement low temperature flexibility, thermotolerance, anti-UV, anti-ozone and good electrical insulating property, and rubber sponge also has light weight, damping and heat insulation characteristics in addition.Domestic and external very big to the demand of silica-gel sponge, be mainly used in fields such as national defence, electronics, aviation, electric locomotive, building, have a extensive future.The silicon rubber foam working method is to add chemical foaming agent (organic type and mineral-type) in the silicone rubber compounds, and whipping agent decomposes the generation bubble in the high temperature vulcanized process, and bubble is wrapped in and forms cavernous structure in the rubber.A kind of in addition novel method is used the platinum addition vulcanization exactly, uses water as whipping agent.
The above-mentioned novel method of mentioning uses water as whipping agent, and complex process is difficult to control, less stable; Simultaneously, use the platinum addition vulcanization, cost is higher, so large-scale promotion production is restricted.Usually rubber sponge mainly uses processing stability and gas forming amount stability organic type of whipping agent preferably, like Cellmic C 121, and dinitrosopentamethylene tetramine etc.Wherein, the Cellmic C 121 gas forming amount is excessive, and is subject to the influence of moisture in the rubber and then hinders sulfuration, makes cavernous structure inhomogeneous simultaneously; Dinitrosopentamethylene tetramine is cheap, and gas forming amount is also big, but the by product that decomposes has strong peculiar smell, and inflammable, is difficult to control.
On the other hand, the foaming of ZGK 5 sponge was many in the past with AIBN (Diisopropyl azodicarboxylate), and each molecular weight of AIBN receives thermogenetic nitrogen amount bigger, uses the sponge that a little can obtain high foamability.But AIBN generates organic cyanide when decomposing, have certain toxicity, and the safety in utilization of sponge is lower.
Along with the increase of consumption, market is to the requirement of silica-gel sponge proposition environmental protection flame retardant, and additives such as its whipping agent fire retardant must environment-protecting asepsis.
Three, the content of invention
The objective of the invention is to traditional silicon silicon rubber sponge less stable, the foaming inhomogeneous; The sponge foaming is subject to the influence of moisture in environment and the rubber; And the weak point of aspect such as toxic; Provide a kind of and have well than low compression set rate, rebound resilience, flame-proof environmental protection and product surface are smooth, the environmental protection flame retardant silicon rubber foam of uniform in foaming and preparation method thereof
The objective of the invention is to realize like this:
Said composition comprises:
(A), the organopolysiloxane of 100 weight parts, the average mark minor is R
4-2nSiO
n, R can be end such as methyl, vinyl, phenyl or trifluoro propyl and replaces or substituted alkyl, can be identical also can be different;
(B), the organic alkylsulfonyl hydrazides class whipping agent of 5-50 weight part and the inorganic foaming agent sodium hydrogencarbonate of 0.5-20 weight part;
(C), 0.1-5 weight part blowing promotor alum 2KAl (SO
4)
2.10H
2O;
(D), 1-300 weight part reinforcement property silicon-dioxide;
(E), make an amount of vulcanizing agent of A composition sulfidization molding;
(F), 10-100 weight part environment friendly flame retardant;
Details are as follows for technical scheme of the present invention:
(A) organopolysiloxane of 100 weight parts.The average mark minor is R
4-2nSiO
n, R can be end such as methyl, vinyl, phenyl or trifluoro propyl and replaces or substituted alkyl, can be identical also can be different.Preferable methyl, vinyl, and contents of ethylene is best at 0.05-0.5% in preferred.Contents of ethylene has very big influence to sulfuration and cross-linked rubber thermotolerance, and low excessively then effect is not remarkable; The too high thermotolerance that then reduces cross-linked rubber.
(B) the present invention uses organic alkylsulfonyl hydrazides class whipping agent, and can and use with inorganic foaming agent.
Organic alkylsulfonyl hydrazides class whipping agent can be benzol sulfohydrazide, two benzol sulfohydrazide ethers, p-toluene sulfonyl hydrazide, Toluene-2,4-diisocyanate, 4-disulfonyl hydrazide, phenyl-1,3 sulfonyl hydrazide etc.Preferred benzol sulfohydrazide, two benzol sulfohydrazide ethers.Disperse for convenient, the common oil component is prefabricated into pasty state.The organic blowing agent weight part is 5-50 part, preferred 10-45 weight part.
Sodium hydrogencarbonate is different with bicarbonate of ammonia, inferior ammonium nitrate and nitrine class inorganic foaming agent, can not be decomposed to form strong acid and highly basic, and does not have pungent smell.The sodium hydrogencarbonate gas forming amount is big simultaneously, and a small amount of interpolation can form the higher sponge of expansion ratio.The inorganic foaming agent weight part is 0.5-20 part, preferred 1-15 weight part.
(C) 0.1-5 weight part blowing promotor alum 2KAl (SO
4)
2.10H
2Both sexes hydrates such as O
Alum 2KAl (SO
4)
2.10H
2O is the both sexes hydrate, if adsorption moisture in rubber heat treatment process or the environment, hydrolysis itself then forms aluminum hydroxide gel with moisture absorption owing to the existence of alum, and white lake can also play fire-retardant effect simultaneously; After alum was evenly distributed in rubber, chance heat dried out and forms gas, plays foaming effect.
(D) 1-300 weight part reinforcement property silicon-dioxide;
For making silicon rubber foam obtain physical strength preferably, utilize silicon-dioxide to gain in strength.Can be thermal silica, precipitated silica, preferred thermal silica.Preferred 150～the 400m of its specific surface area
2/ g.Available a kind of, but also two or more and usefulness, and usage quantity is the 1-300 weight part, preferred 1-200 weight part.
(E) make an amount of vulcanizing agent of A composition sulfidization molding;
Make the vulcanizing agent of A composition sulfidization molding can be Lucidol, 2,4-dichlorobenzoperoxide, t-butylperoxyl benzoate, di-t-butyl peroxide, Di Cumyl Peroxide 99,2,5-dimethyl--2, organo-peroxides such as 5-di-t-butyl hexane peroxide.Select wherein one or both for use and use.When selecting one of which, selecting umber (mass parts) for use is 0.5-15;
(F) 10-100 weight part environment friendly flame retardant;
Environment friendly flame retardant comprises: oxyhydroxide class, boracic class and contain the molybdenum class; Be white lake, Marinco H, zinc borate, molybdic oxide etc., preferred mass part 10-100 part.
Environmental protection flame retardant silicon rubber foam of the present invention, its preparation method:
(1), on twin-screw extruder, prepare sizing material by component:
(2), with A component about 10～20min that on opening rubber mixing machine, plasticates, add the D component, mixing to color even, after the smooth surface thin logical 5～8 times, following sheet;
(3), oven temperature is set in 100～400 ℃, with rubber unvulcanizate thermal treatment 0.5～4h, place afterwards and store 24～96h under the room temperature condition;
(4), the rubber unvulcanizate 0.5～2h after the back mixing thermal treatment, add E component and F component by a certain percentage, after mixing; Add B component and C component, remix is even, the about 10mm of slice thickness; Place in 100～300 ℃ the baking oven behind the about 5～30min of hot-air vulcanization, obtain silicon rubber foam.
Environmental protection flame retardant silicon rubber foam provided by the invention, it has:
1, smooth surface is smooth, and the aperture is even, and surface skining thickness is moderate and even.
2, foam sponge durometer level (sponge sclerometer) 15～40, tensile strength is not less than 6kg/cm
2, 25% compression load, 0.3～0.8kg/cm;
3, according to relevant criterion test, foam sponge fire retardant rank reaches V0 level (flame retardant rating is by HB in the standard, and V-2, V-1, V-0 increases progressively step by step, V-0 is high flame retardant grade).
Most preferred embodiment of the present invention:
Instance 1:
Be the organopolysiloxane of the 500g of 0.3mol% about 10min that on opening rubber mixing machine, plasticates with contents of ethylene, the adding specific surface area is 180m
3The thermal silica 25g of/g, mixing to color even, approach following sheet after the smooth surface logical 5～8 times; Oven temperature is set in 250 ℃, with rubber unvulcanizate thermal treatment 0.5h, places afterwards and stores 96h under the room temperature condition; Rubber unvulcanizate 0.5h after the back mixing thermal treatment adds 2,5-dimethyl--2; 5-di-t-butyl hexane peroxide 3g, white lake 50g is after it is mixed; Add two benzol sulfohydrazide ether 50g, sodium hydrogencarbonate 10g and alum 1g, remix is even, the about 10mm of slice thickness; Place in 250 ℃ the baking oven behind the about 10min of hot-air vulcanization, obtain silicon rubber foam.
Instance 2:
The organopolysiloxane that with contents of ethylene is the 500g of 0.25mol% was plasticated on opening rubber mixing machine about 10min hour, and the adding specific surface area is 380m
3The thermal silica 30g of/g, mixing to color even, approach following sheet after the smooth surface logical 5～8 times; Oven temperature is set in 220 ℃, with rubber unvulcanizate thermal treatment 2h, places afterwards and stores 30h under the room temperature condition; Rubber unvulcanizate 0.5h after the back mixing thermal treatment adds 2,5-dimethyl--2; 5-di-t-butyl hexane peroxide 4g, molybdic oxide 55g is after mixing; Add two benzol sulfohydrazide ether 45g, sodium hydrogencarbonate 8g and alum 0.8g, remix is even, the about 10mm of slice thickness; Place in 250 ℃ the baking oven behind the about 10min of hot-air vulcanization, obtain silicon rubber foam.
It is following that instance 1 and instance 2 make the effect list of foamed silastic sponge:
Claims (7)
1. environmental protection flame retardant silicon rubber foam, said composition comprises:
(A), the organopolysiloxane of 100 weight parts, the average mark minor is R
4-2nSiO
n, R can be end such as methyl, vinyl, phenyl or trifluoro propyl and replaces or substituted alkyl, can be identical also can be different;
(B), the organic alkylsulfonyl hydrazides class whipping agent of 5-50 weight part and the inorganic foaming agent sodium hydrogencarbonate of 0.5-20 weight part;
(C), 0.1-5 weight part blowing promotor alum 2KAl (SO
4)
2.10H
2O
(D), 1-300 weight part reinforcement property silicon-dioxide;
(E), make an amount of vulcanizing agent of A composition sulfidization molding;
(F), 10-100 weight part environment friendly flame retardant.
2. environmental protection flame retardant silicon rubber foam as claimed in claim 1, wherein preferable methyl, vinyl in (A) composition, and contents of ethylene be the best at 0.05-0.5% in preferred.
3. environmental protection flame retardant silicon rubber foam as claimed in claim 1, the preferred 10-45 weight part of organic blowing agent in (B) composition wherein, the preferred 1-15 weight part of inorganic foaming agent.
4. environmental protection flame retardant silicon rubber foam as claimed in claim 1, wherein (D) composition MR medium reinforcing property silicon-dioxide can be thermal silica, precipitated silica, preferred thermal silica, the preferred 150-400m of its specific surface area
2/ g; Available a kind of, but also two or more and usefulness, and usage quantity is the 1-300 weight part, preferred 1-200 weight part.
5. environmental protection flame retardant silicon rubber foam as claimed in claim 1, wherein the vulcanizing agent in (E) composition can be Lucidol, 2; The 4-dichlorobenzoperoxide, t-butylperoxyl benzoate, di-t-butyl peroxide; Di Cumyl Peroxide 99; 2,5-dimethyl--2, organo-peroxides such as 5-di-t-butyl hexane peroxide; Select wherein one or both for use and use; When selecting one of which, selecting umber (mass parts) for use is 0.5-15.
6. environmental protection flame retardant silicon rubber foam as claimed in claim 1, wherein the environment friendly flame retardant in (F) composition comprises: oxyhydroxide class, boracic class and contain the molybdenum class; Be white lake, Marinco H, zinc borate, molybdic oxide, preferred mass part 10-100 part.
7. environmental protection flame retardant silicon rubber foam as claimed in claim 1, its preparation method:
(1), on twin-screw extruder, prepare sizing material by component:
(2), with A component about 10～20min that on opening rubber mixing machine, plasticates, add the D component, mixing to color even, after the smooth surface thin logical 5～8 times, following sheet;
(3), oven temperature is set in 100～400 ℃, with rubber unvulcanizate thermal treatment 0.5～4h, place afterwards and store 24～96h under the room temperature condition;
(4), the rubber unvulcanizate 0.5～2h after the back mixing thermal treatment, add E component and F component by a certain percentage, after mixing; Add B component and C component, remix is even, the about 10mm of slice thickness; Place in 100～300 ℃ the baking oven behind the about 5～30min of hot-air vulcanization, obtain silicon rubber foam.
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|---|---|---|---|
| CN2011104185056A CN102516770A (en) | 2011-12-13 | 2011-12-13 | Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof |
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|---|---|---|---|
| CN2011104185056A CN102516770A (en) | 2011-12-13 | 2011-12-13 | Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483827A (en) * | 2013-09-16 | 2014-01-01 | 上海旭创高分子材料有限公司 | Inflaming retarding fluorine silica gel |
| CN103849149A (en) * | 2014-03-06 | 2014-06-11 | 汉川市鑫天节能保温材料有限公司 | Polymer composite foam material and preparation method thereof |
| CN106543737A (en) * | 2016-12-06 | 2017-03-29 | 上海新益电力线路器材有限公司 | Cable high-low temperature resistant sheath material, restrictive coating and preparation method thereof |
| CN106589959A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Ultralow-density silicone rubber foam material and preparation method thereof |
| CN106589958A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Silicone-rubber foam material with high heat conductivity and preparation method therefor |
| CN108727824A (en) * | 2018-05-30 | 2018-11-02 | 嘉兴中易碳素科技有限公司 | Height rebound closed pore flame-proof silicon rubber foamed material and preparation method thereof |
| CN109575602A (en) * | 2018-10-29 | 2019-04-05 | 郭跃 | A kind of preparation method of silicon rubber foam |
| CN109762344A (en) * | 2019-01-14 | 2019-05-17 | 东莞市南炬高分子材料有限公司 | A kind of halogen-free flame-retardant expanded silica gel material preparation method |
| CN109825085A (en) * | 2018-12-29 | 2019-05-31 | 易宝（福建）高分子材料股份公司 | A kind of environmental protection flame retardant thermal contraction silicon rubber closed pore molding high temperature second time of foaming material resistant to high temperatures and preparation method thereof |
| CN111154160A (en) * | 2020-01-16 | 2020-05-15 | 郑蕊 | Foamed silica gel material for bra and preparation method thereof |
| CN115926243A (en) * | 2022-08-17 | 2023-04-07 | 常州威斯双联科技有限公司 | Flame-retardant heat-insulation foam aerogel and preparation method thereof |
| CN116285365A (en) * | 2023-03-30 | 2023-06-23 | 东莞市利群榕兴高分子科技有限公司 | Foaming conductive silicon rubber and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483827A (en) * | 2013-09-16 | 2014-01-01 | 上海旭创高分子材料有限公司 | Inflaming retarding fluorine silica gel |
| CN103483827B (en) * | 2013-09-16 | 2016-08-17 | 上海旭创高分子材料有限公司 | Fire-retardant fluorine silica gel |
| CN103849149A (en) * | 2014-03-06 | 2014-06-11 | 汉川市鑫天节能保温材料有限公司 | Polymer composite foam material and preparation method thereof |
| CN106589959A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Ultralow-density silicone rubber foam material and preparation method thereof |
| CN106589958A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Silicone-rubber foam material with high heat conductivity and preparation method therefor |
| CN106543737A (en) * | 2016-12-06 | 2017-03-29 | 上海新益电力线路器材有限公司 | Cable high-low temperature resistant sheath material, restrictive coating and preparation method thereof |
| CN108727824A (en) * | 2018-05-30 | 2018-11-02 | 嘉兴中易碳素科技有限公司 | Height rebound closed pore flame-proof silicon rubber foamed material and preparation method thereof |
| CN109575602A (en) * | 2018-10-29 | 2019-04-05 | 郭跃 | A kind of preparation method of silicon rubber foam |
| CN109825085A (en) * | 2018-12-29 | 2019-05-31 | 易宝（福建）高分子材料股份公司 | A kind of environmental protection flame retardant thermal contraction silicon rubber closed pore molding high temperature second time of foaming material resistant to high temperatures and preparation method thereof |
| CN109762344A (en) * | 2019-01-14 | 2019-05-17 | 东莞市南炬高分子材料有限公司 | A kind of halogen-free flame-retardant expanded silica gel material preparation method |
| CN111154160A (en) * | 2020-01-16 | 2020-05-15 | 郑蕊 | Foamed silica gel material for bra and preparation method thereof |
| CN115926243A (en) * | 2022-08-17 | 2023-04-07 | 常州威斯双联科技有限公司 | Flame-retardant heat-insulation foam aerogel and preparation method thereof |
| CN115926243B (en) * | 2022-08-17 | 2024-04-05 | 常州威斯双联科技有限公司 | Flame-retardant heat-insulating foam aerogel and preparation method thereof |
| CN116285365A (en) * | 2023-03-30 | 2023-06-23 | 东莞市利群榕兴高分子科技有限公司 | Foaming conductive silicon rubber and preparation method thereof |
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Application publication date: 20120627 |