CN104927362A - Flame-retardant ceramization silicon rubber and preparation method - Google Patents
Flame-retardant ceramization silicon rubber and preparation method Download PDFInfo
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- CN104927362A CN104927362A CN201510359220.8A CN201510359220A CN104927362A CN 104927362 A CN104927362 A CN 104927362A CN 201510359220 A CN201510359220 A CN 201510359220A CN 104927362 A CN104927362 A CN 104927362A
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Abstract
The invention relates to flame-retardant ceramization silicon rubber. The flame-retardant ceramization silicon rubber is prepared by the following raw materials in part by weight: 100 parts of methyl vinyl silicone rubber, 30-50 parts of reinforcing agents, 5-15 parts of structure control agents, 0.1-5 parts of silane coupling agents, 1-50 parts of ceramization filling materials, 1-50 parts of zinc borate, 1-50 parts of zinc oxide, 1-50 parts of talcum powder, 0.000001-1 part of platinum complex counted by platinum mass and 0.1-0.5 part of internal releasing agents. The flame-retardant level of the silicon rubber material reaches UL94V-0 level, characteristics of the rubber are kept at normal temperature, the rubber can be subjected to ceramization at high temperature to form a hard ceramic layer, the ceramic layer has certain strength and can bear a certain impact force, and normal operation of products can be guaranteed in a fire hazard.
Description
Technical field
The present invention relates to a kind of silicon rubber, especially a kind of Flame-retardant ceramic silicone rubber, belongs to chemical industrial field.
Background technology
In recent years, the understanding of people to fire hazard is constantly deepened, and especially in electric wire, fire is once occur to cause immeasurable loss to people's lives and properties, and this just has higher requirement to the flame-retarding characteristic of electric wire.At present, the flame resistant cable that the domestic and international mica tape of employing is mostly wound around and magnesium oxide mineral fireproof cable, but mica tape is wound around cable craft complexity, and very easily come off after meeting fiery burning, and magnesium oxide mineral fireproof cable involves great expense, more difficult universal.Ceramic silicon rubber is arisen at the historic moment thus.
Ceramic silicon rubber can form the ceramic layer with some strength after flame ablation, and Halogen, low cigarette, low toxicity, environmental protection, cost are lower, flame resistant cable can well be applied to, but existing several Ceramic silicon rubber in the market, after all there is ablation, ceramic layer intensity is lower, and the shortcoming of flame retardant properties poor (not reaching UL94V-0 level), therefore application is subject to certain restrictions.
Summary of the invention
The object of the invention is, in order to solve the deficiencies in the prior art, to provide a kind of Flame-retardant ceramic silicone rubber, after flame ablation, ceramic layer intensity is higher, Stability Analysis of Structures, and excellent flame retardancy.
The technical scheme that the present invention takes is:
A kind of Flame-retardant ceramic silicone rubber, be made up of the raw material of following parts by weight:
Methyl vinyl silicone rubber 100 parts, strengthening agent 30 ~ 50 parts, constitution controller 5 ~ 15 parts, silane coupling agent 0.1 ~ 5 part, ceramic filler 1 ~ 50 part, zinc borate 1 ~ 50 part, 1 ~ 50 part, zinc oxide, talcum powder 1 ~ 50 part, platinum complex is in platinum quality 0.000001 ~ 1 part and inner pattern releasing agent applicable 0.1 ~ 0.5 part.
Described methyl vinyl silicone rubber contents of ethylene is 0.01% ~ 0.3%, and molecular weight is 40 ~ 800,000; Strengthening agent is the one in thermal silica or precipitated silica; Constitution controller is hydroxy silicon oil; Platinum complex is the complex compound of platinum and divinyl tetramethyl-siloxanes.
As further preferred version, above-mentioned Flame-retardant ceramic silicone rubber, is made up of the raw material of following parts by weight: methyl vinyl silicone rubber 100 parts, strengthening agent 35 ~ 45 parts, constitution controller 5 ~ 10 parts, silane coupling agent 3 ~ 4 parts, ceramic filler 10 ~ 30 parts, zinc borate 3 ~ 25 parts, 3 ~ 25 parts, zinc oxide, talcum powder 3 ~ 25 parts, platinum complex in platinum quality 0.000001 ~ 0.01 part, inner pattern releasing agent applicable 0.1 ~ 0.5 part.
Described strengthening agent is preferably thermal silica, and product strength obtained is like this better.
Described silane coupling agent be selected from aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicon or vinyltrimethoxy silane any one.
Described ceramic filler is any one in mica powder, kaolin or wollastonite.
Described inner pattern releasing agent applicable is any one in stearic acid, Zinic stearas or calcium stearate.
The preparation method of above-mentioned Flame-retardant ceramic silicone rubber, comprises the following steps:
(1) add in kneader by methyl vinyl silicone rubber, strengthening agent, constitution controller, silane coupling agent, inner pattern releasing agent applicable, mediate 1-3h under 150 DEG C ~ 180 DEG C conditions, then discharging, obtains sizing;
(2) sizing is left standstill 12 ~ 48h at 25 ~ 35 DEG C;
(3) toward leave standstill after sizing in add ceramic filler, zinc borate, zinc oxide, talcum powder and platinum complex, in kneader, be then kneaded into agglomerate obtain sizing material, use opening rubber mixing machine by sizing material back mixing, finally filter, to obtain final product.
In step (3), the kneading temperature in kneader is 150 DEG C ~ 180 DEG C, and the time is 0.5-2h, and vacuum tightness is-0.05 to-0.08MPa.
In step (3), during gained filter operation, sizing material is filtered through 300 to 350 mesh filter screens.
In preparation method of the present invention, step (1) is by adding silane coupling agent, and white carbon black generation chemical reaction, forms chemical bond energy and combines, greatly improve the physicals of sizing material; Step (2) carries out standing technique after obtaining basic glue, experimental result shows that basic glue is placed after 12 to 48h leaves standstill process can make thermal silica surface hydroxyl be processed preferably, make thermal silica and rubber mixing more evenly, the material resources performances such as the tear resistance of raising rubber unvulcanizate and resistance to deformation; The zinc borate, zinc oxide and the talcum powder that add in step (3) can reduce the melt temperature of Ceramic silicon rubber, make it form ceramic layer at a lower temperature, and make ceramic layer finer and close, and fire performance improves.
Beneficial effect of the present invention: Flame-retardant ceramic silicone rubber of the present invention, after flame ablation, ceramic layer intensity is higher, Stability Analysis of Structures, and excellent flame retardancy, flame retardant properties can reach UL94 V-0 level.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, for the ease of describing, the methyl vinyl silicone rubber adopted in following embodiment is the 110-2S that Dong Jue organosilicon company limited produces, and hydroxy silicon oil is the JS-209 that Liyang Jushen Technology Material Co., Ltd. produces.Should understand these embodiments to be only not used in for illustration of the present invention and to limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims limited range.
Embodiment 1
By methyl vinyl silicone rubber 100 parts, precipitated silica 35 parts, hydroxy silicon oil 5 parts, vinyltrimethoxy silane 4 parts, Zinic stearas 0.2 part adds kneader, mediates 2h, then discharging, obtain sizing under 160 DEG C of conditions; By sizing at 25 DEG C of standing 24h; Toward leave standstill after sizing in add kaolin 20 parts, zinc borate 4 parts, 8 parts, zinc oxide, platinum complex, in platinum quality 0.00001 part, is kneaded into agglomerate and obtains sizing material in kneader, and temperature rises to 160 DEG C and vacuumizes 1h, vacuum tightness is-0.05 to-0.08MPa, then use the sizing material back mixing that opening rubber mixing machine will mix, gained sizing material filters through 300 mesh filter screens, obtains Ceramic silicon rubber.
Embodiment 2
By methyl vinyl silicone rubber 100 parts, thermal silica 35 parts, hydroxy silicon oil 10 parts, aminopropyl triethoxysilane 4 parts, Zinic stearas 0.2 part adds kneader, mediates 2h, then discharging, obtain sizing under 160 DEG C of conditions; By sizing at 25 DEG C of standing 24h; Toward leave standstill after sizing in add kaolin 25 parts, zinc borate 4 parts, 8 parts, zinc oxide, platinum complex, in platinum quality 0.00001 part, is kneaded into agglomerate and obtains sizing material in kneader, and temperature rises to 180 DEG C and vacuumizes 1h, vacuum tightness is-0.05 to-0.08MPa, then use the sizing material back mixing that opening rubber mixing machine will mix, gained sizing material filters through 300 mesh filter screens, obtains Ceramic silicon rubber.
Embodiment 3
By methyl vinyl silicone rubber 100 parts, thermal silica 35 parts, hydroxy silicon oil 10 parts, glycidyl ether oxygen propyl trimethoxy silicon 4 parts, calcium stearate 0.2 part adds kneader, mediates 2h, then discharging, obtain sizing under 160 DEG C of conditions; By sizing at 25 DEG C of standing 18h; Toward leave standstill after sizing in add wollastonite 24 parts, zinc borate 3 parts, 10 parts, zinc oxide, platinum complex, in platinum quality 0.00001 part, is kneaded into agglomerate and obtains sizing material in kneader, and temperature rises to 180 DEG C and vacuumizes 1h, vacuum tightness is-0.05 to-0.08MPa, then use the sizing material back mixing that opening rubber mixing machine will mix, gained sizing material filters through 300 mesh filter screens, obtains Ceramic silicon rubber.
Embodiment 4
By methyl vinyl silicone rubber 100 parts, thermal silica 35 parts, hydroxy silicon oil 10 parts, vinyltrimethoxy silane 4 parts, Zinic stearas 0.2 part adds kneader, mediates 2h, then discharging, obtain sizing under 160 DEG C of conditions; By sizing at 25 DEG C of standing 24h; Toward leave standstill after sizing in add wollastonite 12 parts, zinc borate 8 parts, 4 parts, zinc oxide, talcum powder 12 parts, platinum complex is in platinum quality 0.00001 part, in kneader, be kneaded into agglomerate obtain sizing material, temperature rises to 180 DEG C and vacuumizes 1h, and vacuum tightness is-0.05 to-0.08MPa, then uses the sizing material back mixing that opening rubber mixing machine will mix, gained sizing material filters through 300 mesh filter screens, obtains Ceramic silicon rubber.
Performance test
The Ceramic silicon rubber obtained by embodiment and domestic Ceramic silicon rubber carry out performance test comparison, and test data sees the following form:
Note: two two or five add-ons of vulcanizing agent are 1% of Ceramic silicon rubber, and curing temperature is 175 DEG C, and mechanical property 2mm sample curing time is 300s, and electrical property 1mm sample curing time is 180s, and fire-retardant sample 3mm sample curing time is 420s.
Test data as can be seen from upper table: the Ceramic silicon rubber that the embodiment of the present invention obtains, compared with domestic Ceramic silicon rubber, has better flame retardant properties and more excellent ceramic effect.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a Flame-retardant ceramic silicone rubber, is characterized in that, is made up of the raw material of following parts by weight:
Methyl vinyl silicone rubber 100 parts, strengthening agent 30 ~ 50 parts, constitution controller 5 ~ 15 parts, silane coupling agent 0.1 ~ 5 part, ceramic filler 1 ~ 50 part, zinc borate 1 ~ 50 part, 1 ~ 50 part, zinc oxide, talcum powder 1 ~ 50 part, platinum complex is in platinum quality 0.000001 ~ 1 part and inner pattern releasing agent applicable 0.1 ~ 0.5 part;
Described methyl vinyl silicone rubber contents of ethylene is 0.01% ~ 0.3%, and molecular weight is 40 ~ 800,000; Strengthening agent is the one in thermal silica or precipitated silica; Constitution controller is hydroxy silicon oil; Platinum complex is the complex compound of platinum and divinyl tetramethyl-siloxanes.
2. Flame-retardant ceramic silicone rubber as claimed in claim 1, is characterized in that, be made up of the raw material of following parts by weight:
Methyl vinyl silicone rubber 100 parts, strengthening agent 35 ~ 45 parts, constitution controller 5 ~ 10 parts, silane coupling agent 3 ~ 4 parts, ceramic filler 10 ~ 30 parts, zinc borate 3 ~ 25 parts, 3 ~ 25 parts, zinc oxide, talcum powder 3 ~ 25 parts, platinum complex in platinum quality 0.000001 ~ 0.01 part, inner pattern releasing agent applicable 0.1 ~ 0.5 part.
3. Flame-retardant ceramic silicone rubber as claimed in claim 1, it is characterized in that, described strengthening agent is thermal silica.
4. Flame-retardant ceramic silicone rubber as claimed in claim 1, is characterized in that, described silane coupling agent be selected from aminopropyl triethoxysilane, glycidyl ether oxygen propyl trimethoxy silicon or vinyltrimethoxy silane any one.
5. Flame-retardant ceramic silicone rubber as claimed in claim 1, is characterized in that, described ceramic filler is any one in mica powder, kaolin or wollastonite.
6. the Flame-retardant ceramic silicone rubber according to any one of claim 1 to 5, is characterized in that, described inner pattern releasing agent applicable is any one in stearic acid, Zinic stearas or calcium stearate.
7. the preparation method of the Flame-retardant ceramic silicone rubber described in any one of claim 1 to 6, is characterized in that, comprises the following steps:
(1) add in kneader by methyl vinyl silicone rubber, strengthening agent, constitution controller, silane coupling agent, inner pattern releasing agent applicable, mediate 1-3h under 150 DEG C ~ 180 DEG C conditions, then discharging, obtains sizing;
(2) sizing is left standstill 12 ~ 48h at 25 ~ 35 DEG C;
(3) toward leave standstill after sizing in add ceramic filler, zinc borate, zinc oxide, talcum powder and platinum complex, in kneader, be then kneaded into agglomerate obtain sizing material, use opening rubber mixing machine by sizing material back mixing, finally filter, to obtain final product.
8. the preparation method of Flame-retardant ceramic silicone rubber as claimed in claim 7, it is characterized in that, in step (3), the kneading temperature in kneader is 150 DEG C ~ 180 DEG C, and the time is 0.5-2h, and vacuum tightness is-0.05 to-0.08MPa.
9. the preparation method of Flame-retardant ceramic silicone rubber as claimed in claim 7 or 8, is characterized in that, in step (3), filtered by sizing material during gained filter operation through 300 to 350 mesh filter screens.
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| CN105238065A (en) * | 2015-11-03 | 2016-01-13 | 深圳市沃尔核材股份有限公司 | Liquid ceramic silicone rubber and preparation method thereof |
| CN105566832A (en) * | 2016-01-29 | 2016-05-11 | 苏州诚晟信息技术有限公司 | Silicone rubber for wires and cables |
| CN105623273A (en) * | 2015-10-30 | 2016-06-01 | 深圳市沃尔核材股份有限公司 | Coatable ceramic silicone rubber and preparation method therefor |
| CN105860536A (en) * | 2016-04-13 | 2016-08-17 | 山东兆圭高分子材料科技有限公司 | Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof |
| CN106046797A (en) * | 2016-06-02 | 2016-10-26 | 沈阳化工大学 | Ceramic silicon rubber and preparation method thereof |
| CN106102196A (en) * | 2016-05-30 | 2016-11-09 | 沈兴线缆集团有限公司 | A kind of well rod adds electric heating cable and manufacture method thereof |
| CN106398231A (en) * | 2016-09-14 | 2017-02-15 | 东莞市朗晟硅材料有限公司 | Ceramic fire-resistant and flame-retardant silicone rubber and preparation method thereof |
| CN106751909A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | A kind of odorlessness bi-component addition type Flame-retardant ceramic silicone rubber and preparation method thereof |
| CN107501946A (en) * | 2017-09-05 | 2017-12-22 | 成都众高材科技有限公司 | A kind of ceramic fire-resistant functionality inserts and its production and use |
| CN108022673A (en) * | 2017-11-16 | 2018-05-11 | 东莞市朗晟硅材料有限公司 | A kind of fire resistant flexible branch cable of the anti-spray of antidetonation |
| CN108587181A (en) * | 2018-03-21 | 2018-09-28 | 上海大学 | One kind can porcelain SiClx rubber thermally protective materials and preparation method thereof |
| CN109370229A (en) * | 2018-08-10 | 2019-02-22 | 江苏双汇电力发展股份有限公司 | A kind of ultra-high-voltage post composite insulator rubber compound and preparation method thereof |
| CN109448912A (en) * | 2018-12-12 | 2019-03-08 | 宋局 | A kind of protective-cover type flame retardant cable |
| CN110016231A (en) * | 2019-04-26 | 2019-07-16 | 常州市沃科科技有限公司 | Fire-resistant silicon rubber and preparation method thereof, conducting wire |
| CN110066515A (en) * | 2019-04-02 | 2019-07-30 | 上海新益电力线路器材有限公司 | A kind of protective cover material, fire resistant flame retardant cable and preparation method thereof |
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| CN110183858A (en) * | 2019-07-11 | 2019-08-30 | 中山市华南理工大学现代产业技术研究院 | It is a kind of can selfreparing Ceramic silicon rubber material and preparation method thereof |
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| CN105623273A (en) * | 2015-10-30 | 2016-06-01 | 深圳市沃尔核材股份有限公司 | Coatable ceramic silicone rubber and preparation method therefor |
| CN105238065A (en) * | 2015-11-03 | 2016-01-13 | 深圳市沃尔核材股份有限公司 | Liquid ceramic silicone rubber and preparation method thereof |
| CN105566832A (en) * | 2016-01-29 | 2016-05-11 | 苏州诚晟信息技术有限公司 | Silicone rubber for wires and cables |
| CN105860536A (en) * | 2016-04-13 | 2016-08-17 | 山东兆圭高分子材料科技有限公司 | Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof |
| CN106102196A (en) * | 2016-05-30 | 2016-11-09 | 沈兴线缆集团有限公司 | A kind of well rod adds electric heating cable and manufacture method thereof |
| CN106046797A (en) * | 2016-06-02 | 2016-10-26 | 沈阳化工大学 | Ceramic silicon rubber and preparation method thereof |
| CN106398231A (en) * | 2016-09-14 | 2017-02-15 | 东莞市朗晟硅材料有限公司 | Ceramic fire-resistant and flame-retardant silicone rubber and preparation method thereof |
| CN106751909A (en) * | 2017-01-13 | 2017-05-31 | 山东船舶技术研究院 | A kind of odorlessness bi-component addition type Flame-retardant ceramic silicone rubber and preparation method thereof |
| CN107501946A (en) * | 2017-09-05 | 2017-12-22 | 成都众高材科技有限公司 | A kind of ceramic fire-resistant functionality inserts and its production and use |
| CN108022673A (en) * | 2017-11-16 | 2018-05-11 | 东莞市朗晟硅材料有限公司 | A kind of fire resistant flexible branch cable of the anti-spray of antidetonation |
| CN108587181A (en) * | 2018-03-21 | 2018-09-28 | 上海大学 | One kind can porcelain SiClx rubber thermally protective materials and preparation method thereof |
| CN109370229A (en) * | 2018-08-10 | 2019-02-22 | 江苏双汇电力发展股份有限公司 | A kind of ultra-high-voltage post composite insulator rubber compound and preparation method thereof |
| CN109448912A (en) * | 2018-12-12 | 2019-03-08 | 宋局 | A kind of protective-cover type flame retardant cable |
| CN110066515A (en) * | 2019-04-02 | 2019-07-30 | 上海新益电力线路器材有限公司 | A kind of protective cover material, fire resistant flame retardant cable and preparation method thereof |
| CN110157191A (en) * | 2019-04-04 | 2019-08-23 | 上海新益电力线路器材有限公司 | Refractory protection component and preparation method thereof for wire and cable |
| CN110016231A (en) * | 2019-04-26 | 2019-07-16 | 常州市沃科科技有限公司 | Fire-resistant silicon rubber and preparation method thereof, conducting wire |
| CN110183858A (en) * | 2019-07-11 | 2019-08-30 | 中山市华南理工大学现代产业技术研究院 | It is a kind of can selfreparing Ceramic silicon rubber material and preparation method thereof |
| CN110452540A (en) * | 2019-08-15 | 2019-11-15 | 中山市创达有机硅材料有限公司 | A kind of flame-resistant high-temperature-resistant ceramic glue and preparation method thereof |
| CN111154160A (en) * | 2020-01-16 | 2020-05-15 | 郑蕊 | Foamed silica gel material for bra and preparation method thereof |
| CN112210217A (en) * | 2020-09-28 | 2021-01-12 | 东莞海之澜硅胶科技有限公司 | Anti-vibration ceramic silicon rubber and preparation method thereof |
| CN113122180A (en) * | 2021-04-20 | 2021-07-16 | 浙江清优材料科技有限公司 | Fireproof ceramic organosilicon foaming sealant and preparation method thereof |
| CN115819981A (en) * | 2022-12-14 | 2023-03-21 | 安徽东爵有机硅有限公司 | High-strength low-smoke flame-retardant silicone rubber compound and preparation method thereof |
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