CN102367322A - ABS (acrylonitrile butadiene styrene) halogen-free flame-retardant composite material and preparation method thereof - Google Patents
ABS (acrylonitrile butadiene styrene) halogen-free flame-retardant composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ABS (acrylonitrile butadiene styrene) halogen-free flame-retardant composite material. The ABS halogen-free flame-retardant composite material comprises the following raw material components in parts by weight: 80-100 parts of acrylonitrile-butadiene-styrene copolymer, 40-55 parts of composite flame retardant, 5-12 parts of synergistic flame retardant, 1-5 parts of organic clay, 0.1-0.5 part of antioxidant, 1-3 parts of lubricating agent and 3-7 parts of compatilizer. The ABS halogen-free flame-retardant composite material prepared by the method provided by the invention has the characteristics of good flame retardance and excellent mechanical property and processing performance.
Description
Technical field
The present invention relates to polymeric material field, especially a kind of ABS halogen-free flame-retardant composite material and preparation method thereof.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS) is the extremely wide universal thermoplastic engineering plastic of a kind of application, is vinyl cyanide, divinyl, vinylbenzene three monomeric terpolymers.(with the polyhutadiene is main chain by graft copolymer for it; With vinylbenzene, acrylonitrile copolymer is side chain), the random copolymers (AS resin) of vinylbenzene and vinyl cyanide and not three kinds of staples of the free divinyl of grafted constitute, so it is not merely this three kinds of monomeric multipolymers or mixture.ABS resin not only has toughness, hardness, the good mechanical property of rigidity phase isostatic; And have performances such as chemical proofing, dimensional stability, surface gloss, low temperature tolerance characteristics, tinctorial property and processing fluidity preferably, can be widely used in fields such as electronic apparatus, communications and transportation, material of construction.Yet, along with the continuous enhancing of human environment protection consciousness, to the requirement of above-mentioned field material therefor flame retardant properties also increasingly stringent.This just makes that very easily incendiary ABS has received huge restriction and challenge on using, and the flame retardant resistance that how to improve and improve ABS has become the problem that various countries competitively solve.
For a long time, the flame-retardant modified of ABS is main to add halide-containing (like decabromodiphenyl oxide, eight bromo ether, tetrabromo-bisphenol, brominated epoxy resin oligopolymer etc.) and antimony compounds (like Antimony Trioxide: 99.5Min).This halogenated flame retardant is owing to low price, and flame retarding efficiency height and excellent cost performance make it in fire-retardant market, be in dominant position all the time.Yet the Halogen fire retardant material time can produce a large amount of smog and poisonous, corrosive gas in burning, and the velocity of diffusion of gas is much larger than flame, thereby causes serious " secondary disaster ".Therefore develop the compound fire-retardant and environmental protection requirement certainly of fire retardant material of Halogen.But packing type halogen-free flame retardantss such as employed Marinco H, white lake, expanded graphite, red phosphorus in the prior art, the too high severe exacerbation of fire retardant addition main mechanical property and the processing characteristics of ABS.Therefore, it is high to develop a kind of flame retardant properties, and the ABS composite flame-proof material of good mechanical performance becomes the urgent demand in market simultaneously.
Summary of the invention
The present invention will propose a kind of ABS halogen-free flame-retardant composite material with excellent mechanical performances and processing characteristics and preparation method thereof in order to solve the problems of the technologies described above.
The technical scheme that the present invention adopted is: it is following that a kind of ABS halogen-free flame-retardant composite material, feed composition are pressed the mass fraction proportioning:
Acrylonitrile-butadiene-styrene copolymer 80-100 part,
Composite flame-retardant agent 40-55 part,
Synergistic flame retardant 5-12 part,
The clay 1-5 part that organises,
Oxidation inhibitor 0.1-0.5 part,
Lubricant 1-3 part,
Compatilizer 3-7 part.
In preferred embodiment of the present invention, described acrylonitrile-butadiene-styrene copolymer is synthetic by the suspension-s graft copolymerization, and specific density is 1.0-1.1g/cm3, and butadiene content is 17-70%.
In preferred embodiment of the present invention, described composite flame-retardant agent comprises carbon source and acid source, and the mass ratio of carbon source and acid source is 2:3, and wherein said carbon source is a high-polymerization degree ammonium phosphate, and described acid source is the polyamide 6 of polyamide 6 and modification.
In preferred embodiment of the present invention, described synergistic flame retardant is the 4A molecular sieve.
In preferred embodiment of the present invention, the described clay that organises for the loess that organises, the laterite or the pearl opal mineral that organise organise.
In preferred embodiment of the present invention, described oxidation inhibitor is 2,2-methylene-bis (4-methyl-6-tert butyl phenol), (3,5-di-t-butyl-4-hydroxyl-phenyl) vinylformic acid pentaerythritol ester, antioxidant 1010 or triphenyl phosphite.
In preferred embodiment of the present invention, described lubricant is the two hard esteramides of ethylene group, glyceryl monostearate or Tristearoylglycerol.
In preferred embodiment of the present invention, described compatilizer is the grafts of ABS and maleic anhydride, and percentage of grafting is 0.5-3%.
The invention also discloses a kind of preparation method of BS halogen-free flame-retardant composite material, described making step is:
(1) takes by weighing raw material according to the mass fraction proportioning;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Add composite flame-retardant agent, synergistic flame retardant again, the clay that organises, oxidation inhibitor, lubricant and compatilizer; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
Beneficial effect of the present invention is:
1, the present invention adopts composite flame-retardant agent, and wherein carbon source is a high-polymerization degree ammonium phosphate, and described acid source is the polyamide 6 of polyamide 6 and modification, and being equipped with the 4A molecular sieve again is that synergistic flame retardant constitutes the flame retardant properties that halogen-free flame-retardant system has significantly improved the ABS matrix material.
2, the present invention has added the clay that organises, compatilizer on the basis of composite flame-retardant agent, has improved the mechanical property and the machining property of matrix material, thereby has improved the application performance of matrix material.
Embodiment
Combine embodiment that the present invention is done further detailed explanation now.
It is following that a kind of ABS halogen-free flame-retardant composite material, feed composition are pressed the mass fraction proportioning:
Acrylonitrile-butadiene-styrene copolymer 80-100 part,
Composite flame-retardant agent 40-55 part,
Synergistic flame retardant 5-12 part,
The clay 1-5 part that organises,
Oxidation inhibitor 0.1-0.5 part,
Lubricant 1-3 part,
Compatilizer 3-7 part.
Wherein, acrylonitrile-butadiene-styrene copolymer is synthetic by the suspension-s graft copolymerization, and specific density is 1.0-1.1g/cm3, and butadiene content is 17-70%; Composite flame-retardant agent comprises carbon source and acid source, and the mass ratio of carbon source and acid source is 2:3, and wherein said carbon source is a high-polymerization degree ammonium phosphate, and described acid source is the polyamide 6 of polyamide 6 and modification; Described synergistic flame retardant is the 4A molecular sieve; The described clay that organises for the loess that organises, the laterite or the pearl opal mineral that organise organise; Described oxidation inhibitor is 2,2-methylene-bis (4-methyl-6-tert butyl phenol), (3,5-di-t-butyl-4-hydroxyl-phenyl) vinylformic acid pentaerythritol ester, antioxidant 1010 or triphenyl phosphite; Described lubricant is the two hard esteramides of ethylene group, glyceryl monostearate or Tristearoylglycerol; Described compatilizer is the grafts of ABS and maleic anhydride, and percentage of grafting is 0.5-3%.
A kind of preparation method of BS halogen-free flame-retardant composite material, making step is:
(1) takes by weighing raw material according to the mass fraction proportioning;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Add composite flame-retardant agent, synergistic flame retardant again, the clay that organises, oxidation inhibitor, lubricant and compatilizer; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
Embodiment 1
A kind of preparation method of BS halogen-free flame-retardant composite material, making step is:
(1) takes by weighing raw material according to the mass fraction proportioning: synthetic by the suspension-s graft copolymerization; Specific density is 1.0-1.1g/cm3; Butadiene content be 17-70% 55 parts of 80 parts of acrylonitrile-butadiene-styrene copolymers, composite flame-retardant agents (wherein; 22 parts in high-polymerization degree ammonium phosphate, 10 parts of polyamide 6s, 23 parts of the polyamide 6s of modification), 5 parts in 4A molecular sieve, 1 part of loess organises; 2,3 parts of the two hard esteramides of 0.5 part of 2-methylene-bis (4-methyl-6-tert butyl phenol), ethylene group, percentage of grafting are 7 parts of the graftss of ABS and the maleic anhydride of 0.5-3%;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Add composite flame-retardant agent, 4A molecular sieve, the loess that organises, 2 again; 2-methylene-bis (4-methyl-6-tert butyl phenol), the two hard esteramides of ethylene group and percentage of grafting are the ABS of 0.5-3% and the grafts of maleic anhydride; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
Embodiment 2
A kind of preparation method of BS halogen-free flame-retardant composite material, making step is:
(1) takes by weighing raw material according to the mass fraction proportioning: synthetic by the suspension-s graft copolymerization; Specific density is 1.0-1.1g/cm3; Butadiene content be 17-70% 50 parts of 90 parts of acrylonitrile-butadiene-styrene copolymers, composite flame-retardant agents (wherein; 20 parts in high-polymerization degree ammonium phosphate; 15 parts of polyamide 6s, 15 parts of polyamide 6s of modification), 9 parts in 4A molecular sieve, 3 parts in the laterite of organising, 0.3 part of antioxidant 1010,2 parts of glyceryl monostearates, percentage of grafting are 5 parts of the graftss of ABS and the maleic anhydride of 0.5-3%;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Adding composite flame-retardant agent, 4A molecular sieve, the laterite that organises, antioxidant 1010, glyceryl monostearate and percentage of grafting again is the ABS of 0.5-3% and the grafts of maleic anhydride; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
Embodiment 3
A kind of preparation method of BS halogen-free flame-retardant composite material, making step is:
(1) takes by weighing raw material according to the mass fraction proportioning: synthetic by the suspension-s graft copolymerization; Specific density is 1.0-1.1g/cm3; Butadiene content be 17-70% 40 parts of 100 parts of acrylonitrile-butadiene-styrene copolymers, composite flame-retardant agents (wherein; 16 parts in high-polymerization degree ammonium phosphate; 14 parts of polyamide 6s, 10 parts of polyamide 6s of modification), 12 parts in 4A molecular sieve, 5 parts of the pearl opal mineral of organising, 0.1 part of triphenyl phosphite, 1 part of Tristearoylglycerol, percentage of grafting are 3 parts of the graftss of ABS and the maleic anhydride of 0.5-3%;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Add composite flame-retardant agent, 4A molecular sieve again, organise pearl opal mineral, triphenyl phosphite, Tristearoylglycerol and percentage of grafting are the ABS of 0.5-3% and the grafts of maleic anhydride; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and through above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification sheets, must confirm its technical scope according to the claim scope.
Claims (9)
1. an ABS halogen-free flame-retardant composite material is characterized in that, it is following that feed composition is pressed the mass fraction proportioning:
Acrylonitrile-butadiene-styrene copolymer 80-100 part,
Composite flame-retardant agent 40-55 part,
Synergistic flame retardant 5-12 part,
The clay 1-5 part that organises,
Oxidation inhibitor 0.1-0.5 part,
Lubricant 1-3 part,
Compatilizer 3-7 part.
2. ABS halogen-free flame-retardant composite material according to claim 1 is characterized in that, described acrylonitrile-butadiene-styrene copolymer is synthetic by the suspension-s graft copolymerization, and specific density is 1.0-1.1g/cm3, and butadiene content is 17-70%.
3. ABS halogen-free flame-retardant composite material according to claim 1; It is characterized in that described composite flame-retardant agent comprises carbon source and acid source, the mass ratio of carbon source and acid source is 2:3; Wherein said carbon source is a high-polymerization degree ammonium phosphate, and described acid source is the polyamide 6 of polyamide 6 and modification.
4. ABS halogen-free flame-retardant composite material according to claim 1 is characterized in that, described synergistic flame retardant is the 4A molecular sieve.
5. ABS halogen-free flame-retardant composite material according to claim 1 is characterized in that, the described clay that organises for the loess that organises, the laterite or the pearl opal mineral that organise organise.
6. ABS halogen-free flame-retardant composite material according to claim 1; It is characterized in that described oxidation inhibitor is 2,2-methylene-bis (4-methyl-6-tert butyl phenol); (3,5-di-t-butyl-4-hydroxyl-phenyl) vinylformic acid pentaerythritol ester, antioxidant 1010 or triphenyl phosphite.
7. ABS halogen-free flame-retardant composite material according to claim 1 is characterized in that, described lubricant is the two hard esteramides of ethylene group, glyceryl monostearate or Tristearoylglycerol.
8. ABS halogen-free flame-retardant composite material according to claim 1 is characterized in that, described compatilizer is the grafts of ABS and maleic anhydride, and percentage of grafting is 0.5-3%.
9. the preparation method of an ABS halogen-free flame-retardant composite material is characterized in that, described making step is:
(1) takes by weighing raw material according to the mass fraction proportioning;
(2) alkene nitrile-BS is added preheating 5min in the Banbury mixer; Add composite flame-retardant agent, synergistic flame retardant again, the clay that organises, oxidation inhibitor, lubricant and compatilizer; At 180-185 ℃, melt blending 10-15min under the 50-60r/min condition;
(3) again with melt blended material with compression molding agent preheating 3-5min, then at 180-185 ℃, under the 14-15MPa behind the hot pressing 6-7min, the 3-5min that under 14-15MPa, colds pressing, moulding.
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| CN103183959A (en) * | 2013-04-10 | 2013-07-03 | 苏州旭光聚合物有限公司 | Reinforced flame-retardant PA6 (polyamide)/ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
| CN103951928A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Flame-retardation acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN104962034A (en) * | 2015-07-31 | 2015-10-07 | 广东轻工职业技术学院 | Modified halogen-free flame retardant ABS composition and preparation method thereof |
| CN105733172A (en) * | 2016-05-09 | 2016-07-06 | 安徽江淮汽车股份有限公司 | High-performance ABS alloy and preparation method thereof |
| CN105885333A (en) * | 2016-05-09 | 2016-08-24 | 安徽江淮汽车股份有限公司 | Flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN106543630A (en) * | 2016-10-25 | 2017-03-29 | 安徽别格迪派标识系统有限公司 | A kind of flame-proof heat-resistant type automobile plastic uptake material of containing mesopore molecular sieve Graphene and preparation method thereof |
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| CN106566182A (en) * | 2016-10-25 | 2017-04-19 | 安徽别格迪派标识系统有限公司 | Mesoporous molecular sieve-graphene-containing antibacterial and flame-retardant automobile plastic sucking material and preparation method thereof |
| CN110003604A (en) * | 2019-04-23 | 2019-07-12 | 常州工程职业技术学院 | A kind of ABS flame retardant composite material and preparation method thereof using the preparation of acrylic artificial stone waste material |
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| CN103183959A (en) * | 2013-04-10 | 2013-07-03 | 苏州旭光聚合物有限公司 | Reinforced flame-retardant PA6 (polyamide)/ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof |
| CN103951928A (en) * | 2014-04-02 | 2014-07-30 | 合肥杰事杰新材料股份有限公司 | Flame-retardation acrylonitrile-butadiene-styrene composite material and preparation method thereof |
| CN104962034A (en) * | 2015-07-31 | 2015-10-07 | 广东轻工职业技术学院 | Modified halogen-free flame retardant ABS composition and preparation method thereof |
| CN105733172A (en) * | 2016-05-09 | 2016-07-06 | 安徽江淮汽车股份有限公司 | High-performance ABS alloy and preparation method thereof |
| CN105885333A (en) * | 2016-05-09 | 2016-08-24 | 安徽江淮汽车股份有限公司 | Flame-retardant ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN106543630A (en) * | 2016-10-25 | 2017-03-29 | 安徽别格迪派标识系统有限公司 | A kind of flame-proof heat-resistant type automobile plastic uptake material of containing mesopore molecular sieve Graphene and preparation method thereof |
| CN106543631A (en) * | 2016-10-25 | 2017-03-29 | 安徽别格迪派标识系统有限公司 | A kind of flame retardant automotive plastic uptake material of containing mesopore molecular sieve Graphene and preparation method thereof |
| CN106566182A (en) * | 2016-10-25 | 2017-04-19 | 安徽别格迪派标识系统有限公司 | Mesoporous molecular sieve-graphene-containing antibacterial and flame-retardant automobile plastic sucking material and preparation method thereof |
| CN110003604A (en) * | 2019-04-23 | 2019-07-12 | 常州工程职业技术学院 | A kind of ABS flame retardant composite material and preparation method thereof using the preparation of acrylic artificial stone waste material |
| CN114539713A (en) * | 2022-04-20 | 2022-05-27 | 山东海科创新研究院有限公司 | Synergistic flame retardant, flame-retardant ABS composite material and preparation method thereof |
| CN114539713B (en) * | 2022-04-20 | 2023-08-11 | 山东海科创新研究院有限公司 | Synergistic flame retardant, flame-retardant ABS composite material and preparation method thereof |
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Application publication date: 20120307 |