CN101759952A - Halogen-free flame-retardant and thermoplastic composite - Google Patents
Halogen-free flame-retardant and thermoplastic composite Download PDFInfo
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- CN101759952A CN101759952A CN200810220313A CN200810220313A CN101759952A CN 101759952 A CN101759952 A CN 101759952A CN 200810220313 A CN200810220313 A CN 200810220313A CN 200810220313 A CN200810220313 A CN 200810220313A CN 101759952 A CN101759952 A CN 101759952A
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Abstract
The present invention discloses a halogen-free flame-retardant and thermoplastic composite. The composite consists of constituents of the following percentages by weight: 65 to 90% of rubber modified polymer material containing styrene and acrylonitrile, 5 to 30% of red phosphorus master batch and 0 to 5% of melamine cyanurate. The halogen-free flame-retardant and thermoplastic composite can exhibit good flame-retardant effect by only adopting the red phosphorus master batch, and the melamine cyanurate flame retardant can also be compounded as an auxiliary. The use amount of both the flame retardant and charring agent is small.
Description
Technical field
The field of the invention is the thermoplastic compound material field of halogen-free flameproof, and specifically, the present invention has realized containing the good halogen-free flameproof performance of polymkeric substance of vinylbenzene, propylene cyanogen and modified rubber.
Background technology
The polymer materials that contains cinnamic modified rubber has the excellent processing characteristics and the balance of mechanical property, is applied in electronics/electric, household electrical appliances, IT, office equipment, automobile and other industries widely.But because in various application occasions, the influence that the material of using as structure units such as housings is subjected to thermal source may cause burning, in these occasions material is proposed the requirement of flame retardant properties, and the assessment of flame retardant properties is with reference to the respective standard of UL 94 usually.
In the plastics flame retardant area, the synergistic flame retardant that adopts bromated fire retardant usually and contain stibium trioxide reaches good flame retardancy.Yet recent discovers, many bromated fire retardants such as Poly Brominated Diphenyl Ethers/Polybrominated biphenyl etc. produce deleterious carcinogenic substance such as dioxy (mixing) glutinous rehmannia and furans etc. in burning or Cheng Zhonghui.Some bromide fire retardant has been forbidden in some international organizations and European Union market.And bromated fire retardant also exists the corrosion mould, degradation defective under the thermal stability of material.Therefore wish by developing phosphonium flame retardant and even siliceous fire retardant so that the deficiency of being mentioned above overcoming.
At present, in ABS halogen-free flameproof field, there has been a large amount of work to utilize the fire retardant of phosphorus system or phosphorus nitrogen system.In this field, general view is to use the flame-retardant system of phosphorus system to be difficult to reach good flame-retardant effect merely, therefore, usually to add the material that helps into charcoal such as polycarbonate, polyphenylene oxide or nylon etc., with the deficiency of the one-tenth charcoal aspect that remedies ABS resin.
Chinese patent CN 101125949A has announced the ABS/PA alloy of a kind of micro encapsulation red phosphorus and trimeric cyanamide urea hydrochlorate (MCA) cooperative flame retardant, and the addition that its nylon addition is 5wt%～20wt%.MCA is 5wt%～15wt%.
U.S. Pat 6838497B2 has announced the mixture of the modified rubber that contains vinyl cyanide and styrene monomer that organic phosphorus flame retardant is fire-retardant.The addition of its char-forming agent polyphenylene oxide is at 5wt%～60wt%.
Chinese patent CN1616545 announces the method with a kind of halogen-free flame retardant ABS, and its fire retardant is the phosphoric acid ester fire retardant, and its char-forming agent is polyphenylene oxide and Resins, epoxy.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of with the red phosphorus master batch as fire retardant, flame retardant effect is good, the fire retardant consumption is few, the char-forming agent consumption is seldom halogen-free flame-retardant and thermoplastic composite also.
To achieve these goals, the present invention adopts following technical scheme:
A kind of halogen-free flame-retardant and thermoplastic composite, form by the component of following weight percentage:
The polymer materials that contains vinylbenzene and vinyl cyanide 65%～90% of modified rubber;
Red phosphorus master batch 5%～30%;
Trimeric cyanamide urea hydrochlorate 0%～5%.
In above-mentioned halogen-free flame-retardant and thermoplastic composite, the described polymer materials that contains vinylbenzene and vinyl cyanide is preferably ABS resin.
In above-mentioned halogen-free flame-retardant and thermoplastic composite, described rubber is preferably one or more the mixture in polybutadiene rubber, styrene-butadiene rubber(SBR), the nitrile rubber, and the content of rubber accounts for mixture gross weight 10%～20%.
In above-mentioned halogen-free flame-retardant and thermoplastic composite, described red phosphorus master batch is to be the micro encapsulation red phosphorus master batch of matrix coating with nylon, polyphenylene oxide or resol.The coating of red phosphorus can make red phosphorus have smaller particle size, to such an extent as to can be good at being distributed in the matrix and keep its stability.Matrix used purpose is in order to make mixture have better one-tenth charcoal characteristic, and can better consistency be arranged with other component of mixture.
In above-mentioned halogen-free flame-retardant and thermoplastic composite, trimeric cyanamide urea hydrochlorate and red phosphorus master batch can compositely use, even if but the situation that the red phosphorus master batch uses alone also can reach the flame retardant rating of UL 94V-0, add trimeric cyanamide urea hydrochlorate and can improve flame retardant effect.
The preparation method of halogen-free flame-retardant and thermoplastic composite comprises the steps:
(1) each component is mixed in proportion batching, extrudes in twin screw extruder and cooling, granulation and drying, extrusion temperature is set at 190 ℃～250 ℃;
(2) material of extruding pelletization plastifies in injection moulding machine and moulding, and the forming mould temperature is 30 ℃～80 ℃, and injecting machine material tube temperature is set at 200 ℃～240 ℃.
Compared with prior art, the present invention has following beneficial effect:
Halogen-free flame-retardant and thermoplastic composite of the present invention just adopts the red phosphorus master batch just can reach good flame-retardant effect, and can composite trimeric cyanamide urea hydrochlorate fire retardant, and the fire retardant consumption is few, and the char-forming agent consumption also seldom.
Embodiment
Following per-cent is weight percentage.
Embodiment 1
The prescription proportion of composing of the mixture of halogen-free flameproof is as follows: the ABS resin addition is 80% (the polybutadiene rubber content in the ABS resin is 15%), is the red phosphorus master batch 20% of matrix micro encapsulation with nylon.Material is mixed extruding pelletization according to above prescription.The flame retardant rating test is carried out according to the standard of UL 94.The flame retardant rating of material can reach 2.0mm V-0 and 3.0mm V-0.
Embodiment 2
The prescription proportion of composing of the mixture of halogen-free flameproof is as follows: the ABS resin addition is 82% (the styrene-butadiene rubber(SBR) content in the ABS resin is 10%), is the red phosphorus master batch 15wt% of matrix micro encapsulation with nylon, trimeric cyanamide urea hydrochlorate 3%.Material is mixed extruding pelletization according to above prescription.The flame retardant rating test is carried out according to the standard of UL 94.The flame retardant rating of material can reach 2.0mm V-0 and 3.0mm V-0.
Embodiment 3
The prescription proportion of composing of the mixture of halogen-free flameproof is as follows: the ABS resin addition is 75% (the nitrile rubber content in the ABS resin is 20%), is the red phosphorus master batch 20% of matrix micro encapsulation with nylon.Material is mixed extruding pelletization according to above prescription.The flame retardant rating test is carried out according to the standard of UL 94.The flame retardant rating of material can reach 2.0mm V-0 and 3.0mm V-0.
Claims (6)
1. halogen-free flame-retardant and thermoplastic composite is characterized in that being made up of the component of following weight percentage:
The polymer materials that contains vinylbenzene and vinyl cyanide 65%～90% of modified rubber;
Red phosphorus master batch 5%～30%;
Trimeric cyanamide urea hydrochlorate 0%～5%.
2. halogen-free flame-retardant and thermoplastic composite as claimed in claim 1 is characterized in that the described polymer materials that contains vinylbenzene and vinyl cyanide is an ABS resin.
3. halogen-free flame-retardant and thermoplastic composite as claimed in claim 1 is characterized in that described rubber is one or more the mixture in polybutadiene rubber, styrene-butadiene rubber(SBR), the nitrile rubber, and the content of rubber accounts for mixture gross weight 10%～20%.
4. halogen-free flame-retardant and thermoplastic composite as claimed in claim 1 is characterized in that described red phosphorus master batch is for being the red phosphorus master batch of matrix micro encapsulation with nylon, polyphenylene oxide or resol.
5. halogen-free flame-retardant and thermoplastic composite as claimed in claim 1 is characterized in that described anti-dripping agent is the anti-dripping agent that acrylate coats.
6. the preparation method of the described halogen-free flame-retardant and thermoplastic composite of claim 1 is characterized in that comprising the steps:
(1) each component is mixed in proportion batching, extrudes in twin screw extruder and cooling, granulation and drying, extrusion temperature is set at 190 ℃～250 ℃;
(2) material of extruding pelletization plastifies in injection moulding machine and moulding, and the forming mould temperature is 30 ℃～80 ℃, and injecting machine material tube temperature is set at 200 ℃～240 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220313A CN101759952A (en) | 2008-12-23 | 2008-12-23 | Halogen-free flame-retardant and thermoplastic composite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220313A CN101759952A (en) | 2008-12-23 | 2008-12-23 | Halogen-free flame-retardant and thermoplastic composite |
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| Publication Number | Publication Date |
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| CN101759952A true CN101759952A (en) | 2010-06-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200810220313A Pending CN101759952A (en) | 2008-12-23 | 2008-12-23 | Halogen-free flame-retardant and thermoplastic composite |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101941A (en) * | 2010-12-30 | 2011-06-22 | 金发科技股份有限公司 | Flame-retarding polyphenyl ether composite, and preparation method and use thereof |
| CN102617972A (en) * | 2012-03-19 | 2012-08-01 | 上海锦湖日丽塑料有限公司 | Halogen-free flame-retardant styrene-series resin composition and preparation method thereof |
| CN102775814A (en) * | 2012-08-10 | 2012-11-14 | 四川省精细化工研究设计院 | Method for preparing micro-encapsulation red phosphorus |
| CN103160058A (en) * | 2011-12-13 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame retardant ABS resin and preparation method thereof |
| CN105037866A (en) * | 2015-04-28 | 2015-11-11 | 桐城市新丰彩印包装有限公司 | Degradable thin film preparation process |
-
2008
- 2008-12-23 CN CN200810220313A patent/CN101759952A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101941A (en) * | 2010-12-30 | 2011-06-22 | 金发科技股份有限公司 | Flame-retarding polyphenyl ether composite, and preparation method and use thereof |
| CN102101941B (en) * | 2010-12-30 | 2012-10-10 | 金发科技股份有限公司 | Flame-retarding polyphenyl ether composite, and preparation method and use thereof |
| CN103160058A (en) * | 2011-12-13 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame retardant ABS resin and preparation method thereof |
| CN102617972A (en) * | 2012-03-19 | 2012-08-01 | 上海锦湖日丽塑料有限公司 | Halogen-free flame-retardant styrene-series resin composition and preparation method thereof |
| CN102775814A (en) * | 2012-08-10 | 2012-11-14 | 四川省精细化工研究设计院 | Method for preparing micro-encapsulation red phosphorus |
| CN102775814B (en) * | 2012-08-10 | 2014-03-19 | 四川省精细化工研究设计院 | Method for preparing micro-encapsulation red phosphorus |
| CN105037866A (en) * | 2015-04-28 | 2015-11-11 | 桐城市新丰彩印包装有限公司 | Degradable thin film preparation process |
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Application publication date: 20100630 |