CN101121796A - Polymer-base flame-proof composite material - Google Patents
Polymer-base flame-proof composite material Download PDFInfo
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- CN101121796A CN101121796A CNA2006101067682A CN200610106768A CN101121796A CN 101121796 A CN101121796 A CN 101121796A CN A2006101067682 A CNA2006101067682 A CN A2006101067682A CN 200610106768 A CN200610106768 A CN 200610106768A CN 101121796 A CN101121796 A CN 101121796A
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- black lead
- expansible black
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Abstract
The invention discloses a polymer-based flame retardant composite material. The polymer-based flame retardant composite material of the invention includes the polymer and the expandable graphite; therein, the expandable graphite is the expandable graphite whose expansion volume is above mL per gram at the expansion temperature of 280 Celsius system; the polymer is the polymer whose melting point is below 250 Celsius system. The polymer can be one of or the mixture of a plurality of the polyethylene, the polypropylene, the polystyrene and styrene copolymer, the polyamide 6, the polybutylene terephthalate and rubber. The rubber can be one of or the mixture of a plurality of the butadiene rubber, natural rubber, styrene butadiene rubber, isoamyl rubber, ethylene propylene rubber, butyl rubber, nitrile rubber and neoprene rubber. The weight shares of the expandable graphite can be 10 to 35 percent. The polymer-based flame retardant composite material of the invention has the good flame retardant properties; at the same time, the cost is low; the invention is easy to promote and use.
Description
One, technical field
The present invention relates to a kind of polymer matrix composite, particularly relate to a kind of polymer-base flame-proof composite material.
Two, background technology
Polymer-base flame-proof composite material is the important focus of polymer modification.The fire retardant that uses has bromide fire retardant, nitrogen flame retardant, organic phosphorus flame retardant, inorganic phosphorus flame retardant, expansion type flame retardant etc.
Expansible black lead is subjected to high heat effect, and the high power expansion can take place rapidly, as expands 200～300 times, can be used as expansion type flame retardant.But in fact, (or allowance for expansion is 200～300mL/g) high temperature expansible black lead just to expand 200～300 times when adopting 900 ℃ of swelling temperatures, the oxygen index of the polymkeric substance/expansible black lead matrix material of preparation is not high, and this polymkeric substance/expansible black lead matrix material is not the good matrix material of flame retardant properties.The commercially available prod all is these type high temp expansible black lead products at present, its high temperature (900 ℃) allowance for expansion is 200～300mL/g, swelling temperature generally need just can reach more than the 200mL/g by allowance for expansion more than 450 ℃, but their expansion multiples under low swelling temperature are all very low, allowance for expansion is below 50mL/g during such as 300 ℃ of swelling temperatures, and this class expansible black lead is not good fire retardant.Such as, adopt this high temperature expansible black lead to be used for polyacrylic composite flame-proof, even the quality consumption of expansible black lead is also also bad to 30% o'clock flame retardant effect, the oxygen index of polypropylene/expansible black lead matrix material only about 22%.
Three, summary of the invention
The object of the present invention is to provide the polymer-base flame-proof composite material that a kind of expansible black lead consumption is few, flame retardant properties is excellent, product cost is low.
The technical scheme that realizes the object of the invention is: a kind of polymer-base flame-proof composite material, comprise polymkeric substance and expansible black lead, wherein expansible black lead is the expandable graphite at low-temperature of allowance for expansion more than 200mL/g when 280 ℃ of swelling temperatures, and polymkeric substance is that fusing point is lower than 250 ℃ polymkeric substance.
In the polymer-base flame-proof composite material of the present invention, polymkeric substance can be one or more the blend in polyethylene, polypropylene, polystyrene and styrol copolymer, polyamide 6, polybutylene terephthalate and the rubber etc.Rubber can be one or more the blend in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, paracril and the chloroprene rubber etc.
In the polymer-base flame-proof composite material of the present invention, the massfraction of expansible black lead can be 10%～35%.
Compared with prior art, the present invention has remarkable advantage.The present invention finds to use when 280 ℃ of swelling temperatures the expandable graphite at low-temperature of allowance for expansion more than 200mL/g as fire retardant, and be used for the fire-retardant compound of polymkeric substance such as polyethylene, polypropylene, polystyrene and styrol copolymer, polyamide 6, polybutylene terephthalate and rubber that fusing point is lower than 250 ℃ or blend, the flame-proof composite material that obtains has excellent flame-retardant, and the consumption of expansible black lead is few and the flame-proof composite material product cost is low.
Four, embodiment
Polymer-base flame-proof composite material of the present invention comprises polymkeric substance and expansible black lead, and wherein expansible black lead is the expandable graphite at low-temperature of allowance for expansion more than 200mL/g when 280 ℃ of swelling temperatures, and polymkeric substance is that fusing point is lower than 250 ℃ polymkeric substance.
Polymer-base flame-proof composite material of the present invention is to be prepared from by melt blending is compound, the fusing point of the polymkeric substance that it adopts should be lower than 250 ℃, it can be one or more the blend in polyethylene, polypropylene, polystyrene and styrol copolymer, polyamide 6, polybutylene terephthalate and the rubber, wherein styrol copolymer can be HIPS, ABS etc., and rubber can be one or more the blend in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, paracril and the chloroprene rubber etc.Certainly, can also be maybe to contain other polymkeric substance that fusing point is lower than 250 ℃.
In the polymer-base flame-proof composite material of the present invention, the massfraction of expansible black lead can be 10%～35%.
With part embodiment invention scheme of the present invention is described below, wherein the expandable graphite at low-temperature of allowance for expansion more than 200mL/g when 280 ℃ of swelling temperatures of Cai Yonging is to get according to Chinese invention patent application CN200410065739.7 " preparation method of expandable graphite at low-temperature " preparation.
Embodiment 1
In expansible black lead: the polypropylene mass ratio is 15: 85 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and polypropylene carry out melting mixing at 185 ℃ and obtain polypropylene/expansible black lead flame-proof composite material, its oxygen index is 25%.
Embodiment 2
In expansible black lead: the polyethylene mass ratio is 25: 75 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 220mL/g and polyethylene carry out melting mixing at 180 ℃ and obtain polyethylene/expansible black lead flame-proof composite material, its oxygen index is 27.5%.
Embodiment 3
In expansible black lead: the polystyrene mass ratio is 30: 70 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 280mL/g and polystyrene carry out melting mixing at 195 ℃ and obtain polystyrene/expansible black lead flame-proof composite material, its oxygen index is 28.5%.
Embodiment 4
In expansible black lead: the ABS mass ratio is 35: 65 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and ABS carry out melting mixing at 195 ℃ and obtain ABS/ expansible black lead flame-proof composite material, its oxygen index is 31%.
Embodiment 5
In expansible black lead: the PA6 mass ratio is 25: 75 a ratio, adopt short length-to-diameter ratio screw extrusion press will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and PA6 carry out melting mixing at 235 ℃ and obtain PA6/ expansible black lead flame-proof composite material, its oxygen index is 26.5%.
Embodiment 6
In expansible black lead: the polybutylene terephthalate mass ratio is 25: 75 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and polybutylene terephthalate carry out melting mixing at 235 ℃ and obtain polybutylene terephthalate/expansible black lead flame-proof composite material, its oxygen index is 26.5%.
Embodiment 7
In expansible black lead: the cis-1,4-polybutadiene rubber mass ratio is 25: 75 a ratio, adopt opening rubber mixing machine will be when 280 ℃ of swelling temperatures allowance for expansion be that expansible black lead and cis-1,4-polybutadiene rubber, vulcanizing agent and the vulcanization aid of 250mL/g carries out the mixing rubber unvulcanizate that makes of low temperature, sulfuration obtains cis-1,4-polybutadiene rubber/expansible black lead flame-proof composite material then, and its oxygen index is 28%.
Embodiment 8
In expansible black lead: polyethylene: the cis-1,4-polybutadiene rubber mass ratio is 20: 65: 15 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and polyethylene, cis-1,4-polybutadiene rubber carry out melting mixing at 180 ℃ and obtain polyethylene/cis-1,4-polybutadiene rubber/expansible black lead flame-proof composite material, its oxygen index is 26.5%.
Embodiment 9
In expansible black lead: polyethylene: the polypropylene mass ratio is 28: 54: 18 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and polyethylene, polypropylene carry out melting mixing at 180 ℃ and obtain polyethylene/polypropylene/expansible black lead flame-proof composite material, its oxygen index is 28.5%.
Embodiment 10
In expansible black lead: cis-1,4-polybutadiene rubber: the styrene-butadiene rubber(SBR) mass ratio is 12: 68: 20 a ratio, adopt opening rubber mixing machine will be when 280 ℃ of swelling temperatures allowance for expansion be that expansible black lead and cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), vulcanizing agent and the vulcanization aid of 250mL/g carries out the mixing rubber unvulcanizate that makes of low temperature, sulfuration obtains cis-1,4-polybutadiene rubber/styrene-butadiene rubber(SBR)/expansible black lead flame-proof composite material then, and its oxygen index is 24.5%.
Comparative example 1
In expansible black lead: the polyethylene mass ratio is 25: 75 a ratio, (900 ℃ of allowance for expansion are 250mL/g with present commercially available expansible black lead product to adopt twin screw extruder, the expansible black lead that several 50 orders of order, the expansion multiple of producing such as Qingdao Ying Shida graphite company limited is 250 times) and polyethylene carry out melting mixing at 180 ℃ and obtain polyethylene/expansible black lead flame-proof composite material, its oxygen index is 22%.
Comparative example 2
In expansible black lead: the PET mass ratio is 30: 70 a ratio, adopt twin screw extruder will be when 280 ℃ of swelling temperatures allowance for expansion be that the expansible black lead of 250mL/g and PET carry out melting mixing at 280 ℃ and obtain PET/ expansible black lead flame-proof composite material, its oxygen index is 22.5%.
Claims (4)
1. polymer-base flame-proof composite material, it is characterized in that: comprise polymkeric substance and expansible black lead, wherein expansible black lead is the expandable graphite at low-temperature of allowance for expansion more than 200mL/g when 280 ℃ of swelling temperatures, and polymkeric substance is that fusing point is lower than 250 ℃ polymkeric substance.
2. polymer-base flame-proof composite material according to claim 1 is characterized in that: polymkeric substance is one or more the blend in polyethylene, polypropylene, polystyrene and styrol copolymer, polyamide 6, polybutylene terephthalate and the rubber.
3. polymer-base flame-proof composite material according to claim 2 is characterized in that: rubber is one or more the blend in natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, ethylene-propylene rubber(EPR), isoprene-isobutylene rubber, paracril and the chloroprene rubber.
4. according to each described polymer-base flame-proof composite material of claim 1～3, it is characterized in that: the massfraction of expansible black lead is 10%～35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101067682A CN101121796A (en) | 2006-06-23 | 2006-08-01 | Polymer-base flame-proof composite material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200610085561.1 | 2006-06-23 | ||
| CNA2006100855611A CN1869118A (en) | 2006-06-23 | 2006-06-23 | Polymer base fire-resistant composite material |
| CNA2006101067682A CN101121796A (en) | 2006-06-23 | 2006-08-01 | Polymer-base flame-proof composite material |
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| CN101121796A true CN101121796A (en) | 2008-02-13 |
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| CNA2006101067682A Pending CN101121796A (en) | 2006-06-23 | 2006-08-01 | Polymer-base flame-proof composite material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323774B (en) * | 2008-07-28 | 2012-07-18 | 公安部四川消防研究所 | Expansion type fireproofing glue strip for construction |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
| CN102807683A (en) * | 2011-06-03 | 2012-12-05 | 北京艾迪泰克技术咨询有限公司 | Method for preparing flame-retardant moulded anti-dripping EPS (expandable polystyrene) foam material |
| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| CN103289397A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Flame-retarding acid-alkali-resistant plastic comprising polyhexamethylene adipamide |
| CN104448447A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Method for preparing environment-friendly low-smoke flame retardant powdered butadiene styrene rubber |
| CN105061839A (en) * | 2015-09-09 | 2015-11-18 | 苏州国泰科技发展有限公司 | Preparation method of flame-retardant rubber |
| CN105295215A (en) * | 2014-07-16 | 2016-02-03 | 江苏业达鑫化工有限公司 | Preparation method for bead-shaped black polystyrene particles |
| CN106893142A (en) * | 2017-03-10 | 2017-06-27 | 北京理工大学 | Surface coating has expansible graphite and its manufacture method, the polymer of titania aerogel |
| CN109231948A (en) * | 2018-09-15 | 2019-01-18 | 四川信衡新型材料科技有限公司 | A kind of light fire-proof composite partition wall plate and preparation method thereof |
| CN109810307A (en) * | 2016-11-02 | 2019-05-28 | 芜湖瑞德机械科技有限公司 | A kind of modified flame-retardant butadiene rubber and preparation method thereof |
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2006
- 2006-08-01 CN CNA2006101067682A patent/CN101121796A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323774B (en) * | 2008-07-28 | 2012-07-18 | 公安部四川消防研究所 | Expansion type fireproofing glue strip for construction |
| CN102807683A (en) * | 2011-06-03 | 2012-12-05 | 北京艾迪泰克技术咨询有限公司 | Method for preparing flame-retardant moulded anti-dripping EPS (expandable polystyrene) foam material |
| CN102604372A (en) * | 2012-02-17 | 2012-07-25 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
| CN102604372B (en) * | 2012-02-17 | 2013-06-05 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
| CN103073862A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Halogen-free flame-retardant polylactic acid nanocomposite and preparation method thereof |
| CN103289397A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Flame-retarding acid-alkali-resistant plastic comprising polyhexamethylene adipamide |
| CN104448447A (en) * | 2013-09-18 | 2015-03-25 | 中国石油天然气股份有限公司 | Method for preparing environment-friendly low-smoke flame retardant powdered butadiene styrene rubber |
| CN105295215A (en) * | 2014-07-16 | 2016-02-03 | 江苏业达鑫化工有限公司 | Preparation method for bead-shaped black polystyrene particles |
| CN105061839A (en) * | 2015-09-09 | 2015-11-18 | 苏州国泰科技发展有限公司 | Preparation method of flame-retardant rubber |
| CN105061839B (en) * | 2015-09-09 | 2016-12-07 | 苏州国泰科技发展有限公司 | A kind of preparation method of flame retardant rubber |
| CN109810307A (en) * | 2016-11-02 | 2019-05-28 | 芜湖瑞德机械科技有限公司 | A kind of modified flame-retardant butadiene rubber and preparation method thereof |
| CN109810307B (en) * | 2016-11-02 | 2021-02-26 | 芜湖乾凯材料科技有限公司 | Modified flame-retardant butadiene rubber and preparation method thereof |
| CN106893142A (en) * | 2017-03-10 | 2017-06-27 | 北京理工大学 | Surface coating has expansible graphite and its manufacture method, the polymer of titania aerogel |
| CN109231948A (en) * | 2018-09-15 | 2019-01-18 | 四川信衡新型材料科技有限公司 | A kind of light fire-proof composite partition wall plate and preparation method thereof |
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Open date: 20080213 |