CN103059499A - Novel inflaming retarding acrylonitrile butadiene styrene copolymer (ABS) composite and preparation method thereof - Google Patents
Novel inflaming retarding acrylonitrile butadiene styrene copolymer (ABS) composite and preparation method thereof Download PDFInfo
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- CN103059499A CN103059499A CN2012105686668A CN201210568666A CN103059499A CN 103059499 A CN103059499 A CN 103059499A CN 2012105686668 A CN2012105686668 A CN 2012105686668A CN 201210568666 A CN201210568666 A CN 201210568666A CN 103059499 A CN103059499 A CN 103059499A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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Abstract
The invention discloses a novel inflaming retarding acrylonitrile butadiene styrene copolymer (ABS) composite and a preparation method thereof. The novel inflaming retarding ABS composite is composed of the following raw materials according to percentage by weight, 68-84% of ABS resin, 10-20% fire retardant, 5-10% of ABS-g-MAH, 0.1-1% of antioxidant, and 0-2% other annexing agent. The novel inflaming retarding ABS composite has the advantages that lignin contained in the novel inflaming retarding ABS composite exists widely and can be easily obtained and be biodegradable. The prepared composite is simple in production process, low in cost and easy to industrialize. On the basic of keeping original mechanical properties of materials, the ABS composite has good inflaming retarding performance.
Description
Technical field
The present invention relates to a kind of novel flame-retardant ABS matrix material and preparation method thereof, belong to polymer modification and processing technique field.
Background technology
ABS plastic has good thermotolerance, and resistance to chemical attack, electrical insulating property and good processibility are widely used in auto parts, the household electrical appliance.Because a lot of occasions all require it to have certain flame retardant properties, all require the flame retardant properties of material to reach UL-94 V-0 level such as flameproof case, switch etc., to improve its safety in utilization.But the flame retardant properties of ABS resin own is very low, and modal method is to add the composite flame retardant system of halogenated flame retardant and antimonous oxide, but it can discharge a large amount of cigarettes and obnoxious flavour when burning, and can damage environment and human body.Simultaneously along with the implementation of the ROHS of European Union instruction and improving constantly of material environment friendly requirement, inorganic combustion inhibitor or phosphorus system, nitrogenated flame retardant obtain certain use, inorganic combustion inhibitor exists flame retarding efficiency low, the problem that addition is large, the phosphorus flame retardant flame retarding efficiency is high, and addition is few, but it makes the material plasticizing, affect the mechanical property of material, limit to a certain extent its use range.
Xylogen is having the important development prospect as a kind of extensive existence, reproducible valuable source aspect preparation degradable, the reproducible polymer composite.The composite polyolefine material of filled with lignin is considered compatibility problem, needs that generally speaking xylogen is carried out adding in modification or the system compatilizer and improves.Because xylogen can be used as a kind of preferably char-forming agent and plays fire retardation, some has been arranged about the research of the flame retardant properties of polyolefine/xylogen at present.Polymer Degradation and Stability, 2012,97,541～546 have reported with phosphorus oxychloride and imidazoles xylogen and have carried out graft modification, improved thermostability and the flame retardant properties of PP/ xylogen, the method needs with an organic solvent, not environmental protection and complex steps.Thermochimica Acta, 2011,518,59～65 have studied content of lignin and compatilizer to the impact of ABS material thermostability and flame retardant properties, but flame retardant effect is limited when using xylogen merely, is difficult to reach the requirement of UL-94 V-0 level.
Summary of the invention
The object of the present invention is to provide that a kind of cost is lower, good flame retardation effect, possess simultaneously novel flame-retardant ABS matrix material of excellent mechanical property and preparation method thereof.
To achieve these goals, novel flame-retardant ABS matrix material of the present invention is comprised of the raw material of following weight percent:
ABS resin 68 ~ 84%,
Fire retardant 10 ~ 20%,
ABS-g-MAH 5~10%，
Oxidation inhibitor 0.1 ~ 1%,
Other additive 0 ~ 2%.
Wherein, described ABS resin is that glue content is the high-impact ABS of 12-20%.
Described fire retardant is the composition of xylogen and halogen-free flame retardants, and wherein xylogen is the wood pulp xylogen, without any modification; Described halogen-free flame retardants is a kind of in phosphorus flame retardant and the nitrogenated flame retardant or their composition.
Described phosphorus flame retardant is a kind of among PDP (Resorcinol biphosphonate), BDP (dihydroxyphenyl propane biphosphonate) and the RDXP (polymkeric substance of RDP); Nitrogenated flame retardant is a kind of among MC (trimeric cyanamide urate) and the MPP (polyphosphoric acid melamine).
The percentage of grafting of described ABS-g-MAH is 0.8 ~ 1.5%.
Described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, and primary antioxidant is the one or more combination in hindered phenol and the sulphur ester antioxidant; Auxiliary anti-oxidant is the one or more combination in phosphite and the ester kind antioxidant.
Described primary antioxidant be 1010,3114 and DSTP in one or more composition; Described auxiliary anti-oxidant is one or more the composition in 168 and 618.
Described other additive is various toner additives or Masterbatch.
Novel flame-retardant ABS composite manufacture method described above is as follows:
(1) takes by weighing by weight ratio raw material;
(2) various raw materials and additive were mixed in super mixer 5 ~ 15 minutes;
(3) mixed raw material is added in the twin screw extruder, the control extrusion temperature is 160 ~ 220 ℃, and preferred 180 ~ 210 ℃, cooling granulation after melt extruding makes the ABS matrix material.
Advantage of the present invention is:
1, the xylogen that uses among the present invention extensively exists, and easily obtains biodegradable.The process for producing composite material of preparation is simple, and cost is low, easily industrialization.
2, the ABS matrix material of the present invention's proposition can on the basis that keeps the original mechanical property of material, have good flame retardant properties.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In embodiment and Comparative Examples composite-material formula, the ABS that described ABS resin selects Taiwan Qi Mei company to produce, commodity by name 747.Used xylogen is the wood pulp xylogen, without any modification.Used phosphorus flame retardant is RDXP.The percentage of grafting of used ABS-g-MAH is 0.8 ~ 1.5%.The DSTP that Britain ICE company produces, commodity be called Negonox DSTP, chemical name is the thio-2 acid octadecyl ester, and Ciba company product 3114, commodity are called Irganox3114, chemical name is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphoric acid.Auxiliary anti-oxidant is 168 of Ciba company product, and commodity are called Irgafos168, and chemical name is three (2,4-di-tert-butyl-phenyl) phosphorous acid ester.Comprise in addition black masterbatch.
Various raw materials and additive are dry mixed 5 ~ 15 minutes in super mixer; The raw material that mixes is added in the twin screw extruder, and through melt extruding, cooling granulation obtains the ABS matrix material.
Performance evaluation mode and implementation standard:
With the particulate material for preparing as stated above, drying is 2～3 hours in 90～100 ℃ convection oven, and then the particulate material that drying is good carries out the injection molding sample preparation at injection moulding machine.
Tensile property test: carry out according to the ISO5271 standard.
Bending property test: carry out according to the ISO178 standard.
Simply supported beam notched Izod impact strength test: carry out according to the ISO179 standard.
Dimension card vicat softening temperature test: carry out according to the ISO306 standard.
Flame retardant properties test: carry out according to the UL-94 standard.
The comprehensive mechanical property of material is passed judgment on by the numerical value of modulus in flexure, notched Izod impact strength and the dimension card vicat softening temperature of test gained.
The prescription of embodiment and Comparative Examples and properties test result are seen lower each table:
Table 1 embodiment 1～5 and Comparative Examples 1～5 material prescription table (% by weight)
Table 2 embodiment 1～5 and Comparative Examples 1～5 test result
Can find out from embodiment 1～5, along with the increase of two kinds of flame retardant agent content, matrix material has still kept good mechanical property to decrease, and Flame Retardancy can then increase to some extent, consider material cost and over-all properties, the fire retardant addition is best about 15%; When system has identical flame retardant agent content, improve the content of xylogen, be conducive to improve the mechanical property of material.Embodiment 1～2 and Comparative Examples 1～5 can find out, when flame retardant agent content was low, although the mechanical property of matrix material is better, the flame retardant properties of material was relatively poor.
Claims (10)
1. novel flame-retardant ABS matrix material, it is characterized in that: the raw material by following weight percent forms:
ABS resin 68 ~ 84%,
Fire retardant 10 ~ 20%,
ABS-g-MAH 5~10%，
Oxidation inhibitor 0.1 ~ 1%,
Other additive 0 ~ 2%.
2. a kind of novel flame-retardant ABS matrix material according to claim 1, it is characterized in that: described ABS resin is that glue content is the high-impact ABS of 12-20%.
3. a kind of novel flame-retardant ABS matrix material according to claim 1, it is characterized in that: described fire retardant is the composition of xylogen and halogen-free flame retardants.
4. a kind of novel flame-retardant ABS matrix material according to claim 3, it is characterized in that: wherein xylogen is the wood pulp xylogen, without any modification; Described halogen-free flame retardants is one or more the composition in phosphorus flame retardant and the nitrogenated flame retardant.
5. a kind of novel flame-retardant ABS matrix material according to claim 4 is characterized in that: described phosphorus flame retardant is a kind of among PDP (Resorcinol biphosphonate), BDP (dihydroxyphenyl propane biphosphonate) and the RDXP (polymkeric substance of RDP); Nitrogenated flame retardant is a kind of among MC (trimeric cyanamide urate) and the MPP (polyphosphoric acid melamine).
6. a kind of novel flame-retardant ABS matrix material according to claim 1, it is characterized in that: the percentage of grafting of described ABS-g-MAH is 0.8 ~ 1.5%.
7. a kind of novel flame-retardant ABS matrix material according to claim 1, it is characterized in that: described oxidation inhibitor comprises primary antioxidant and auxiliary anti-oxidant, primary antioxidant is the one or more combination in hindered phenol and the sulphur ester antioxidant; Auxiliary anti-oxidant is the one or more combination in phosphite and the ester kind antioxidant.
8. a kind of novel flame-retardant ABS matrix material according to claim 7 is characterized in that: described primary antioxidant be 1010,3114 and DSTP in one or more composition; Described auxiliary anti-oxidant is one or more the composition in 168 and 618.
9. a kind of novel flame-retardant ABS matrix material according to claim 1, it is characterized in that: described other additive is various toner additives or Masterbatch.
10. method for preparing the described novel flame-retardant ABS of claim 1 matrix material, it is characterized in that: its concrete steps are as follows:
(1) takes by weighing by weight ratio raw material;
(2) various raw materials were mixed in super mixer 5 ~ 15 minutes;
(3) mixed raw material is added in the twin screw extruder, the control extrusion temperature is 160 ~ 220 ℃, and preferred 180 ~ 210 ℃, cooling granulation after melt extruding makes the ABS matrix material.
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| CN201210568666.8A CN103059499B (en) | 2012-12-24 | 2012-12-24 | A kind of flame-retardant ABS compound material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232640A (en) * | 2013-04-27 | 2013-08-07 | 上海锦湖日丽塑料有限公司 | Spraying-free aesthetic resin composition with amber effect and preparation method thereof |
| CN110483941A (en) * | 2019-09-23 | 2019-11-22 | 聚石化学(苏州)有限公司 | Low 5VA grades of anti-flaming ABS materials of cigarette environmental protection and preparation method thereof |
| CN110591267A (en) * | 2019-09-23 | 2019-12-20 | 聚石化学(苏州)有限公司 | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof |
| CN111100418A (en) * | 2018-10-29 | 2020-05-05 | 普瑞斯玛再生复合材料有限责任公司 | Acrylonitrile butadiene styrene copolymer/lignin blends |
| CN115011063A (en) * | 2022-06-20 | 2022-09-06 | 浙江昊杨新能源科技有限公司 | Chemical modification power battery shell based on lignin |
| CN117644702A (en) * | 2024-01-25 | 2024-03-05 | 保定龙军建材有限公司 | High-performance plastic woven cloth and preparation thereof |
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| CN102250444A (en) * | 2011-07-01 | 2011-11-23 | 江苏技术师范学院 | Halogen-free flame-resistance acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232640A (en) * | 2013-04-27 | 2013-08-07 | 上海锦湖日丽塑料有限公司 | Spraying-free aesthetic resin composition with amber effect and preparation method thereof |
| CN111100418A (en) * | 2018-10-29 | 2020-05-05 | 普瑞斯玛再生复合材料有限责任公司 | Acrylonitrile butadiene styrene copolymer/lignin blends |
| US11708486B2 (en) * | 2018-10-29 | 2023-07-25 | Prisma Renewable Composites, Llc | Acrylonitrile butadiene styrene copolymer/lignin blends |
| CN110483941A (en) * | 2019-09-23 | 2019-11-22 | 聚石化学(苏州)有限公司 | Low 5VA grades of anti-flaming ABS materials of cigarette environmental protection and preparation method thereof |
| CN110591267A (en) * | 2019-09-23 | 2019-12-20 | 聚石化学(苏州)有限公司 | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof |
| CN110483941B (en) * | 2019-09-23 | 2022-04-19 | 聚石化学(苏州)有限公司 | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof |
| CN115011063A (en) * | 2022-06-20 | 2022-09-06 | 浙江昊杨新能源科技有限公司 | Chemical modification power battery shell based on lignin |
| CN117644702A (en) * | 2024-01-25 | 2024-03-05 | 保定龙军建材有限公司 | High-performance plastic woven cloth and preparation thereof |
| CN117644702B (en) * | 2024-01-25 | 2024-04-09 | 保定龙军建材有限公司 | High-performance plastic woven cloth and preparation thereof |
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| CN103059499B (en) | 2016-04-06 |
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