CN1098299C - Fire-retardant room temp. silicon sulfide rubber - Google Patents
Fire-retardant room temp. silicon sulfide rubber Download PDFInfo
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- CN1098299C CN1098299C CN97107706A CN97107706A CN1098299C CN 1098299 C CN1098299 C CN 1098299C CN 97107706 A CN97107706 A CN 97107706A CN 97107706 A CN97107706 A CN 97107706A CN 1098299 C CN1098299 C CN 1098299C
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Abstract
The present invention provides an organic siloxane polymer composition which is composed of 100 portions of polydiorgnosiloxane, 10 to 100 portions of a reinforcing filler, 0.5 to 80 portions of an additive, 3 to 20 portions of a cross-linking agent, 0.01 to 10 portions of a catalyst and 5 to 100 portions of tripolycyanamine cyanurate or/and decabromobiphenyl ether. Fire retarding room temperature silicon sulfurized rubber of the present invention is as superior as the past general silicon rubber in the aspects of heat resisting properties, electrical properties, mechanical strength, etc. The fire retardancy of the present invention reaches the UL94V-O grade; when encountering fire, the fire retarding room temperature silicon sulfurized rubber has favorable excellent self extinguishing properties. The present invention is an ideal insulating material for various household appliances and industrial electric devices.
Description
The present invention relates to a kind of polymeric composition, particularly relate to a kind of single-component constituent polyorganosiloxane composition.
Silicon rubber has various high-performances, but generally it is not fire-retardant, and people have proposed various schemes for it being made the rubber composition of self-extinguishing.What for example, have a representative is to add to contain platinum material in silicon rubber.But only add and contain platinum material not enough, must cooperate other compound.As the gentle phase titanic oxide of platinic compound (special public clear 47-21826), powdery manganous carbonate (spy opens clear 48-84142) and powdery Fe
2O
3The cooperation of (spy opens clear 50-97644) etc.But the self-extinguishing effect of these compositions is very not good, and contains the adding of platinum material, except the thermotolerance that reduces silicone elastomer, under the moisture effect, the electrical property of silicone elastomer is descended.In addition, if when the fleut addition is low, the composition self-extinguishing is poor, and addition is when high, and the mechanical property of silicon rubber descends.
The objective of the invention is to: provide a kind of and have good mechanical strength, electrical insulation capability, self-extinguishing energy, and be not subjected to the single-component flame retardant resistance room temperature vulcanized silicone rubbers that climatope influences, shelf characteric is stable such as humidity.
The objective of the invention is to adopt following scheme to realize: by poly-diorganosiloxane, reinforced filling, additive, linking agent, organic titanium chela thing is or/and in the rubber composition that hydroxy acid metallic tin salt catalyst is formed, the mixture that adds cyanogen urea acid trimeric cyanamide or cyanogen urea acid three polyamine and decabromodiphenyl oxide, make the flame retardant resistance room temperature vulcanized silicone rubber, wherein, the consumption of poly-diorganosiloxane is 100 weight parts, the add-on of reinforced filling is 5～80 weight parts, additive is 0.5～80 weight part, the add-on of linking agent is 1～15 weight part, the addition of catalyzer is 0.05～10 weight part, and the addition of cyanogen urea acid trimeric cyanamide or it and decabromodiphenyl oxide is 6.25～70 weight parts.
Specifically, poly-diorganosiloxane viscosity is homopolymer or the multipolymer of 3000mpa.s～100000mpa.s, and its end group is that hydroxyl or methyl dimethoxy oxygen base are silica-based, and its organic radical is one or more in methyl, phenyl, ethyl, the vinyl.
Reinforced filling is all kinds of silicon-dioxide, and as gas-phase silica, precipitated silica, silica powder, diatomite, its particle diameter is below 50 μ, and specific surface area is greater than 100m
2/ g.In order to make the composition that makes have good physical and mechanical properties and to use technology, generally need carry out chemical treatment to white carbon black, treatment agent can be organosilane, organo-siloxane, or organosilazanes etc.
Additive is light calcium carbonate, titanium dioxide, zinc oxide, carbon black, and its median size is below 50 μ.
Linking agent is an organosilane, and general formula is RSiY
3R is an organic radical, Y is the functional group, as methyltrimethoxy silane, Union carbide A-162, methyl triacetoxysilane, methyl 3 third oximino silanes, methyl tributanoximo silane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, diethylin Union carbide A-162, dioxy Union carbide A-162, six carbon atom and long chain hydrocarbon groups trialkoxy silane, vinyl trialkyl oxysilane.
In the catalyzer: the organic titanium inner complex is transesterify titanium chelate, secondary transesterify titanium chelate, and carboxylic acid metal's pink salt is dibutyl tin dilaurate, dibutyl tin acetate, dibutyl two stannous octoates, Dibutyltin oxide etc.
In the fire retardant: the median size of cyanogen urea acid trimeric cyanamide and decabromodiphenyl oxide is below 50 μ.
In above-mentioned composition, also can add antimonous oxide, aluminium hydroxide, zinc carbonate, zirconium silicate, organic cobalt salt, organo phosphorous compounds, zinc borate etc. one or more, its add-on is 0～25 weight part.
Single-component flame retardant resistance room temperature vulcanized silicone rubber of the present invention is that above-mentioned each component mixing is loaded in the encloses container.During use, contact with airborne moisture with its taking-up and under room temperature, but completely solidified after 2～3 days becomes silicone elastomer.
In the composition of the present invention, poly-diorganosiloxane is given the composition mechanical property as base polymer; Reinforced filling plays the effect that improves the composition mechanical property; The existing certain strengthening action of additive can reduce production costs again; Linking agent can make the crosslinked and curing molding of composition; Catalyzer plays the sulfuration promoter action; Cyanogen urea acid trimeric cyanamide, and it and decabromodiphenyl ether mixture be fire retardant, be the major ingredient of giving the composition self-extinguishing, its addition is during less than 5 weight parts, self-extinguishing weak effect, and when being higher than 100 weight parts, the obvious variation of the processing performance of composition; Antimonous oxide, aluminium hydroxide etc. then are used with fire retardant, both can partly reduce the consumption of cyanogen urea acid trimeric cyanamide, also can improve the flame-retarding characteristic of composition simultaneously.
Single-component flame retardant resistance room temperature vulcanized silicone rubber of the present invention, superior equally at aspects such as thermotolerance, electrical property, physical strength and existing silicon rubber, and its flame retardant properties has really reached the UL94V-0 level, having good self-extinguishing energy when meeting fire, is the desirable insulating material of various household electrical appliances, industrial electric device.
Be embodiments of the invention below, described part is meant weight part.During test performance, be that composition is prepared into the thick mechanical property test piece of 2mm respectively, the electrical property test piece that 1mm is thick, the combustionproperty test piece that 6mm is thick, at room temperature place seven days after, measure its every performance.Wherein flame retardant resistance is to carry out according to the method for UL94 regulation, the thick silicon rubber test piece of the 6mm that is about to vulcanizate, it is long to be cut into 200mm, the standard test piece that 10mm is wide with its vertical fixing, makes the test piece bottom directly contact (the middle place that just places flame) with the blue flame of gaslight, burn after 15 seconds, remove gaslight, measure its self-extinguishing time (second) (for the first time), and then repeat once (for the second time) by last method.
Embodiment one
Get viscosity and be 100 parts of the hydroxyl endblocked polydimethylsiloxanes of 8500mpa.s (under 25 ℃), 22 parts of thermal silicas, 50 parts of the light calcium carbonate of particle diameter below 50 μ, cyanogen urea acid trimeric cyanamide (MCA) 50 parts, 3 parts of titanium dioxide, above mixture is in 100 parts, sneak into 8 parts of the trimethyl silicon based end capped polydimethylsiloxane oligopolymers of thinner, 3 parts of linking agent methyltrimethoxy silanes, 1 part of catalyzer organic titanium huge legendary turtle compound, 0.05 part of dibutyl tin dilaurate, mixing is mixed with single-component room temperature vulcanized silicon rubber (RTV) composition under anhydrous state, preserves in seal tube.
Performance behind the composition hardening is as follows:
Tensile strength: 2.8Mpa; Elongation: 425%; Hardness (HA): 24; Glass cementation shearing resistance: 2.6Mpa; Voltage breakdown: 20.8MV/m; Flame retardant resistance: UL94V-0 level.
Embodiment two
Except linking agent be methyl tributanoximo silane 5 especially, all the other are with embodiment one, performance is as follows behind the composition hardening:
Tensile strength: 2.5Mpa; Elongation: 415%; Hardness (HA): 25; Glass cementation shearing resistance: 2.7Mpa; Voltage breakdown: 20.5MV/m; Flame retardant resistance: UL94V-0 level.
Embodiment three
Except with 3 parts of diethylin Union carbide A-162s, replace outside the methyltrimethoxy silane and organic titanium inner complex among the embodiment one, all the other are with embodiment one.Performance is as follows behind the composition hardening:
Tensile strength: 2.3Mpa; Elongation: 360%; Hardness (HA): 28; Glass cementation shearing resistance: 2.2Mpa; Voltage breakdown: 18.9MV/m; Flame retardant resistance: UL94V-0 level.
Embodiment four
Get viscosity and be 100 parts of the silica-based end capped polydimethylsiloxanes of methyl dimethoxy oxygen base of 9800mpa.s (under 25 ℃), gas-phase silica 16 minutes, 10 parts of the calcium carbonate powders of particle diameter below 50 μ, MCA50 part, 2.5 parts of titanium dioxide, above mixture is in 100 parts, sneak into 5.5 parts of linking agent methyltrimethoxy silanes, 1 part of catalyzer organic titanium inner complex, 0.03 part of dibutyl tin dilaurate are mixed with single-component RTV composition under anhydrous state, preserve in seal tube.
Performance behind the composition hardening is as follows:
Tensile strength: 2.4Mpa; Elongation: 486%; Hardness (HA): 21; Shearing resistance (aluminium-aluminium): 2.1Mpa; Volume resistivity (Ω, cm): 24 * 10
15Dielectric loss angle tangent (60Hz): 45 * 10
-3Specific inductivity (60Hz): 3.0; Voltage breakdown: (MV/m): 21.8; Flame retardant resistance: UL94V-0 level.
Embodiment five
Get viscosity and be 100 parts of the hydroxy-end capped polydimethylsiloxanes of 11500mpa.s (under 25 ℃), specific surface area is 300m
225 parts of the gas-phase silicas of/g, 70 parts of the light calcium carbonate of particle diameter below 50 μ, MCA35 part, 5 parts of titanium dioxide, above mixture is in 100 parts, sneak into 10 parts of thinners, 4 parts of linking agent methyltrimethoxy silanes, 1.5 parts of catalyzer organic titanium inner complexs, 0.04 part of dibutyl tin dilaurate, under anhydrous state, be mixed with rubber composition, be packaged in the seal tube.Its flame retardant properties is the UL94V-1 level.
Embodiment six
The hydroxy-end capped phenyl molar fraction that contains of getting viscosity and be 4500mpa.s (under 25 ℃) is that 0.15 all the other side groups are 100 parts of the poly-diorganosiloxanes of methyl, 55 parts of precipitated silicas, 10 parts in the lime carbonate of particle diameter below 50 μ, cyanogen urea acid trimeric cyanamide (MCA) 70 minutes, 3 parts of titanium dioxide, above mixture is sneaked into 3 parts of diethylin Union carbide A-162s in 100 parts, and performance is as follows behind 6 parts of composition hardenings that make of dichloromethyl triethoxyl silane:
Tensile strength: 2.5Mpa; Elongation: 225%; Hardness (HA): 26; Glass cementation shearing resistance: 2.0Mpa; Voltage breakdown: 18.7MV/m; Flame retardant resistance: UL94V-0 level.
Embodiment seven
Except replace the MCA among the embodiment six with 45 parts of decabromodiphenyl oxides, all the other are with embodiment six.Performance is as follows behind the composition hardening:
Tensile strength: 1.8Mpa; Elongation: 245%; Hardness (HA): 30; Glass cementation is cut intensity: 2.1Mpa; Voltage breakdown: 19MV/m; Flame retardant resistance: UL94V-0 level.
Embodiment eight
Except not adding MCA, all the other carry out fire retardancy test with embodiment four behind the composition hardening, and test piece burns up fully, does not have flame retardant effect.
Embodiment nine
Get viscosity and be 100 parts of the hydroxy-end capped polydimethylsiloxanes of 52500mpa.s (under 25 ℃), specific surface area is 300m
220 parts of the gas-phase silicas of/g, 25 parts of the light calcium carbonate of particle diameter below 50 μ, MCA25 part, 2.5 parts of titanium dioxide, mixing is divided into four parts with said mixture, sneak into 5 parts of antimonous oxides respectively, 15 parts in aluminium hydroxide, 10 parts of decabromodiphenyl oxides, 10 parts of zinc borates (is 100 parts in organopolysiloxane).
Sneak into thinner, linking agent, catalyzer by embodiment four again.Four kinds of composition flame retardant propertiess have all reached the UL94V-1 level.
Claims (8)
1, a kind of single-component flame retardant resistance room temperature vulcanized silicone rubber, by poly-diorganosiloxane, reinforced filling, additive, linking agent, the organic titanium inner complex is or/and hydroxy acid metallic tin salt catalyst composition, it is characterized in that also adding the mixture of cyanogen urea acid trimeric cyanamide or cyanogen urea acid trimeric cyanamide and decabromodiphenyl oxide, wherein, the consumption of poly-diorganosiloxane is 100 parts, the add-on of reinforced filling is 5～80 parts, additive is 0.5～80 part, linking agent is 1～15 part, the total consumption of catalyzer is 0.05～10 part, and the mixture of cyanogen urea acid trimeric cyanamide or cyanogen urea acid trimeric cyanamide and decabromodiphenyl oxide is 6.25～70 parts.
2, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1, it is characterized in that: poly-diorganosiloxane is homopolymer or the multipolymer of viscosity 3000mpa.s～100000mpa.s, its end group is that hydroxyl or methyl dimethoxy oxygen base are silica-based, and its organic radical is one or more in methyl, phenyl, ethyl, the vinyl.
3, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1, it is characterized in that: reinforced filling is all kinds of silicon-dioxide, and as gas-phase silica, silica powder, diatomite, its particle diameter is below 50 μ, and specific surface area is greater than 100m
2/ g.
4, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1, it is characterized in that: additive is light calcium carbonate, titanium dioxide, zinc oxide, carbon black, and its median size is below 50 μ.
5, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1, it is characterized in that: linking agent is an organosilane, general formula is RsiY
3R is an organic radical, Y is the functional group, as methyltrimethoxy silane, Union carbide A-162, methyl triacetoxysilane, methyl 3 third oximino silanes, methyl tributanoximo silane, anilinomethyl triethoxysilane, anilinomethyl trimethoxy silane, diethylin Union carbide A-162, dichloromethyl triethoxyl silane, six carbon atom and long chain hydrocarbon groups trialkoxy silane, vinyl trialkyl oxysilane.
6, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1 is characterized in that: the organic titanium inner complex is that transesterify titanium chelate, secondary transesterify titanium chelate, a hydroxy acid metal pink salt are dibutyl tin dilaurate, dibutyl tin acetate, dibutyl two stannous octoates, Dibutyltin oxide etc. in the catalyst system therefor.
7, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1 is characterized in that: the median size of cyanogen urea acid trimeric cyanamide and decabromodiphenyl oxide is below 50 μ.
8, single-component flame retardant resistance room temperature vulcanized silicone rubber according to claim 1 is characterized in that: also can add antimonous oxide, aluminium hydroxide, and zinc carbonate, zirconium silicate, organic cobalt salt, organo phosphorous compounds, zinc borate etc., its add-on is 0～25 part.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107706A CN1098299C (en) | 1997-10-08 | 1997-10-08 | Fire-retardant room temp. silicon sulfide rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97107706A CN1098299C (en) | 1997-10-08 | 1997-10-08 | Fire-retardant room temp. silicon sulfide rubber |
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| CN1213679A CN1213679A (en) | 1999-04-14 |
| CN1098299C true CN1098299C (en) | 2003-01-08 |
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| CN97107706A Expired - Fee Related CN1098299C (en) | 1997-10-08 | 1997-10-08 | Fire-retardant room temp. silicon sulfide rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101768361B (en) * | 2008-12-30 | 2012-01-11 | 上海回天化工新材料有限公司 | Method for improving room temperature vulcanized silicone rubber mechanical performance |
| CN101564923B (en) * | 2009-05-26 | 2012-03-07 | 武汉理工大学 | Fireproof silicone rubber composite material and preparation method thereof |
| CN101700427B (en) * | 2009-11-20 | 2011-08-17 | 陕西坚瑞消防股份有限公司 | Hot aerosol fire extinguisher with thermostable ablative-insulative layer and manufacture method |
| CN102181263B (en) * | 2011-04-15 | 2013-07-10 | 东莞市科泽新材料科技有限公司 | Flame-retardant dealcoholized sealant for electronic power supply and preparation method thereof |
| CN103951981B (en) * | 2014-05-05 | 2016-08-24 | 中国科学院化学研究所 | A kind of fire-retardant room temperature silicon sulfide rubber composition of phosphorous-silicon polymer and preparation method thereof |
| CN106280479A (en) * | 2016-09-21 | 2017-01-04 | 苏州直角新材料有限公司 | A kind of nano-silicon rubber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162749A (en) * | 1986-12-26 | 1988-07-06 | Nippon Carbide Ind Co Ltd | Flame-retardant non-rigid resin composition |
| EP0543292A1 (en) * | 1991-11-18 | 1993-05-26 | Wacker-Chemie Gmbh | A flame retardant elastomeric composition |
| EP0700962A1 (en) * | 1994-09-07 | 1996-03-13 | Quantum Chemical Corporation | Flame retardant insulation compositions having enhanced curability |
| JPH09132720A (en) * | 1995-09-06 | 1997-05-20 | Toray Ind Inc | Flame retardant resin composition |
-
1997
- 1997-10-08 CN CN97107706A patent/CN1098299C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63162749A (en) * | 1986-12-26 | 1988-07-06 | Nippon Carbide Ind Co Ltd | Flame-retardant non-rigid resin composition |
| EP0543292A1 (en) * | 1991-11-18 | 1993-05-26 | Wacker-Chemie Gmbh | A flame retardant elastomeric composition |
| EP0700962A1 (en) * | 1994-09-07 | 1996-03-13 | Quantum Chemical Corporation | Flame retardant insulation compositions having enhanced curability |
| CN1144236A (en) * | 1994-09-07 | 1997-03-05 | 量子化学公司 | Flame retardant insulation compositions having enhanced curability |
| JPH09132720A (en) * | 1995-09-06 | 1997-05-20 | Toray Ind Inc | Flame retardant resin composition |
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Owner name: SOUTHWEST HUAJI CO., LTD. Free format text: FORMER OWNER: CHENGUANG CHEMICAL RESEARCH ACADEMY (CHENGDU), MINISTRY OF CHEMICAL INDUSTRY Effective date: 20040423 |
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