CN105419218A - Halogen-free flame-retardant reinforced type ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof - Google Patents
Halogen-free flame-retardant reinforced type ABS (acrylonitrile-butadiene-styrene) composite material and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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Abstract
The invention relates to a halogen-free flame-retardant reinforced type ABS (acrylonitrile-butadiene-styrene) composite material and a preparation method thereof, and relates to the technical field of plastics. The halogen-free flame-retardant reinforced type ABS composite material adopts the technical scheme that the halogen-free flame-retardant reinforced type ABS composite material consists of an ABS matrix, a main flame-retardant matrix, a synergic matrix, a reinforced matrix, an anti-dripping agent, an antioxidant, a charring agent, paraffin and a color master batch. The halogen-free flame-retardant reinforced type ABS composite material and the preparation method have the advantages that by utilizing the compounding synergic function of the main flame-retardant matrix, the synergic matrix and the reinforced matrix, the flame-retardant property and mechanical property are good; by compounding inorganic components and organic components, the synergic function is formed, the flame-retardant efficiency and mechanical property of the composite material are improved, and the cost of material is reduced; by using the technology to produce, the technology is simple, the operation is convenient, the production efficiency is improved, and the production cost is reduced; while the property of the composite material is reached, the comprehensive cost is lower than the cost of the traditional ABS composite material.
Description
Technical field
The present invention relates to plastics arts, specifically a kind of flame-retardant reinforced ABS composite material and preparation method thereof.
Background technology
Along with going deep into of social sustainable development idea, the environmental protection of people and awareness of safety have had and have improved largely, also more pay attention to the concern of ecotope and value of life.Present macromolecular material to be lived a necessary part as people, solves the problem that macromolecular material and environmental protection develop in harmony, extremely urgent.Along with people are to the continuous pursuit of quality of the life, make to have higher requirement to plastic raw materials, plastics are just towards future developments such as environmental friendliness, functionalization, low costs, in order to obtain low cost, high-performance and eco-friendly plastics, people more and more pay close attention to and pay attention to the research and apply of plastic material physically modified technology.
ABS resin is the terpolymer of vinyl cyanide (A), divinyl (B), vinylbenzene (S), there is the features such as excellent in cushion effect, heat-resisting and resistance to low temperature is better, and handling ease, be widely used in the industries such as automobile, electronic apparatus, light industry household electrical appliances, but be easy to burning in atmosphere, limiting oxygen index(LOI) is about 18%, and exist without shortcomings such as self-extinguishings, easily drippage, strongly limit its use range, therefore flame-retardant modified having great significance is carried out to it, in recent years the fire-retardant study hotspot having become flame retardance of polymer of ABS.
Halogen flame has the advantages that consumption is little, flame retarding efficiency is high, the flame-proof ABS resin of preparation has good mechanical property, be widely used in the preparation of ABS fire retardant material, but halogen flame produces a large amount of smog and corrosive gases in combustion, the strong carcinogen such as Dioxins (Dioxin) and benzene furans (Benzfuran) can be discharged after halogen flame burning, very easily secondary injury be produced to human body; Simultaneously, the preparation of halogen flame retardant material also can cause the pollution of environment and the corrosion of processing units, promulgation along with European Union RoHS and WEEE instruction limits the application of this flame-retardant system more, selects environmental protection, efficient flame-retarding agent prepares the focus that halogen-free flame retardant ABS material has become research.In research process, when usual halogen-free flame retardants addition reaches a certain amount of, just can reach the requirement of flame retardant rating.And add a large amount of fire retardant, the serious mechanical property that have impact on ABS, being difficult to meet some has the occasion of demand in flame retardant area to mechanical property.Therefore, develop a kind of halogen-free flame-retardant environment-friendly, have excellent mechanical performances again, the ABS composite material simultaneously meeting market demand is again the problem that needs solve.
Summary of the invention
The object of the invention is to overcome the problem that in prior art, ABS material flame retardant properties and mechanical property can not be taken into account very well, a kind of composite synergy by main flame retardant, synergist and reinforcement is provided, and then there is ABS of good flame retardant properties and mechanical property and preparation method thereof.
The technical solution adopted in the present invention is: a kind of halogen-free flameproof reinforced ABS, be made up of ABS matrix, main fire-retardant matrix, synergistic matrix, enhancing matrix, anti-dripping agent, antioxidant, char-forming agent, paraffin and Masterbatch, the parts by weight of each component are followed successively by: ABS matrix 55-70 part, main fire-retardant matrix 10-20 part, synergist matrix 5-8 part, enhancing matrix 10-15 part, char-forming agent 1-5 part, anti-dripping agent 1-2 part, antioxidant 1-2 part, paraffin 1-2 part and look female 1-2 part; Wherein, ABS base rubber content is 40%; Main fire-retardant matrix is by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1-1.5:10, wherein said alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm, described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate; Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, their weight ratio is 3:4:0.5-1:2:10, wherein, described microcapsule red phosphorus median size is 15 μm, and described particle size carbon black is 10nm; Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2, wherein, and described nano silicon purity >99%, median size 10nm, described whisker can be one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker; Described anti-dripping agent is tetrafluoroethylene; Described antioxidant is 1010 or 168 or B219; Char-forming agent is novolac epoxy and OMMT, and form by weight 5:1 blending and modifying, described novolac epoxy epoxy equivalent (weight) is 210, and described OMMT is 400 orders.
Prepare the method for halogen-free flameproof reinforced ABS matrix material, concrete preparation process is:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS base-material according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mixed in (6) and ABS base-material are carried out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
In the present invention, two base hypo-aluminum orthophosphate be phosphorus flame retardant, do not absorb water, the diethyl contained in molecule and ABS resin have good consistency, and simultaneously in molecule, metallic aluminium ion has certain smoke suppressing effect, and decomposes produces PO and P0
2free radical, along with the rising of temperature can generate poly-metaphosphoric acid, PO and PO of generation
2free radical can catch the Active Radicals Produced H0 produced in ABS combustion decomposition process, and poly-metaphosphoric acid is not volatile colloidal cpd, be coated on ABS top layer, effectively cut off oxygen source, stop the transmission of heat, reach fire-retardant effect, poly-metaphosphoric acid is strong dewatering agent simultaneously, forms fine and close carburization zone on ABS surface.
Four-(2,6-xylyl) resorcinol diphosphate are white solid, have the advantages such as good processibility, unique self-extinguishment and good compatibility, do not affect material color and luster simultaneously.With synergistic flame retardant and char-forming agent with the use of when burning, can form one deck layer of charcoal on the surface of ABS, have upright charcoal skeleton to generate after burning, combustionvelocity obviously reduces, and black smoke amount reduces, and melting drip phenomenon disappears.In combustion processes, phosphoric acid ester decompose the phosphoric acid that produces and polyphosphoric acid can and resol between there is crosslinking reaction, promote into charcoal, phosphorus residues in layer of charcoal, and flame retardant effect is more remarkable, and the oxygen index of ABS is significantly improved.Moreover it also has obvious plastification while fire-retardant, improves the plastic flow of ABS, reduces the heat-drawn wire of material.
In the process of burning, synergistic flame retardant trimerization ammonia cyanuric acid, the easy thermal endothermic decomposition of tricyanic acid poly-phosphate discharge the non-flammable gases such as ammonia, nitrogen, water vapor, and meanwhile, most of heat has been taken away in the decomposition of fire retardant, reduces polymer surfaces temperature; The nitrogenous non-flammable gases generated also can react with the oxygen in air and generate nitrogen, water and deep oxidation thing, dilutes the oxygen concn in air and is polymerized the combustable gas concentration decomposing and produce, playing a gas phase iris action.In the process of burning, carbon black plays seizure living radical on the one hand, also plays crosslinked action simultaneously, and increase density and the skeletal support power on layer of charcoal surface, play fire retardation, on the other hand, carbon black also has strengthening action, improves the physical strength of ABS.The microcapsule red phosphorus added can absorb the heat in combustion processes, reduces the decomposition of skin-material, and its pyrolytic decomposition also produces phosphoric acid or metaphosphoric acid simultaneously, is attached to top layer, makes layer of charcoal finer and close.
Resorcinol-bis-(xylenylphosphate) polycondensate, under the acting in conjunction of synergist, has good one-tenth charcoal effect when burning occurs, can reduce rate of release and the Thermal release total amount of ABS significantly.
Novolac epoxy is 40% in the remaining rate of 800 DEG C of charcoals, and the layer of charcoal that burning is formed has certain restraining effect to ABS burning.And under high temperature phosphoric acid ester decompose the phosphoric acid that produces and polyphosphoric acid can and resol between there is crosslinking reaction, promote into charcoal.OMMT is after novolac epoxy intercalation, better disperse in ABS composite material, the layer of charcoal generated during burning is more closely knit, the simultaneously activity of its lamella to polymer molecular chain has significant restriction, thus make polymer molecular chain when decomposes than completely white by molecular chain there is higher decomposition temperature; In addition, being distributed in silicate synusia in polymkeric substance barrier polymer can also decompose the small molecules produced and moves to combustion boundary, also can intercept extraneous oxygen to interface internal migration to reach fire-retardant object simultaneously.
Paraffin has good heat-resistant quality, oxidation stability and light stability, adds gloss and demolding performace that appropriate paraffin is conducive to improving goods.
Modified manometer silicon dioxide and ABS, have good affinity and Physical interaction therebetween; Nano silicon has large specific surface area, can improve tensile property and the Young's modulus of ABS.Modification potassium titanate crystal whisker can be dispersed in ABS matrix, and interwoven mesh structure, plays skeleton function, forms polymkeric substance-metal whisker composite.The existence of modification potassium titanate crystal whisker can form oriented structure, it does not produce anisotropy again simultaneously, reduce the formation of various defect, the stress transfer that can be more effectively subject to by matrix material is to potassium titanate crystal whisker, improve the cohesive strength of matrix material, reduce defect, significantly improve the physical strength of matrix material.The present invention adopts nanoparticle and whisker compound to strengthen ABS, and form " point ", " line " strengthens altogether, larger efficiency improves the mechanical property of material.
Advantage of the present invention is:
1), the present invention adopt inorganic phosphorus fire retardant and organophosphorous fire retardant composite, with under synergistic flame retardant and char-forming agent acting in conjunction, fire retardant addition is few, flame retarding efficiency is high, little to the Effect on Mechanical Properties of matrix material, and environmental nonpollution, belongs to environment friendly flame retardant;
2), novolac epoxy and OMMT blending and modifying in the present invention, improve charring rate after burning on the one hand, improve the flame retardant properties of material, improve the mechanical property of matrix material on the other hand.
3), the present invention adopts potassium titanate crystal whisker, and atomic arrangement is neat, almost can overcome the various defects of polycrystalline material.Because its interface is regular, length-to-diameter ratio is high, intensity is high, structure is very thin and modulus advantages of higher, can be uniformly dispersed in the polymer through modification, play skeletal support effect, form polymkeric substance-metal whisker composite, oriented structure can be formed simultaneously, and don't generation anisotropy, reduce the formation of various defect, the stress transfer that can be more effectively subject to by matrix material is to potassium titanate crystal whisker, improve the cohesive strength of matrix material, reduce defect, significantly improve the physical strength of matrix material.
4), compared with prior art, the present invention adopts nanoparticle and the composite reinforced composite of needle-like whisker, strengthens altogether, improve the various defects in composite modification process comprehensively from " point " to " line ", improve the cohesive strength of material, increase material over-all properties.
5), in the present invention, inorganic component and the composite use of organic constituent, form synergy, improve flame retarding efficiency and the mechanical property of matrix material simultaneously, reduce material cost; Adopt explained hereafter of the present invention, technique is simple, easy to operate simultaneously, and production efficiency, can reduce production cost simultaneously.In a word, while reaching composite property, it is comparatively obvious that comprehensive cost compares to traditional ABS composite material advantage.
embodiment:
Embodiment 1:
ABS matrix 55 parts;
Main fire-retardant matrix 18 parts;
Synergist matrix 7 parts;
Strengthen matrix 14 parts;
Char-forming agent 2 parts;
Anti-dripping agent 1 part;
Antioxidant 1 part;
1 part, paraffin and look female 1 part.
Wherein:
ABS base rubber content is 40%;
Main fire-retardant matrix is by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1.5:10, wherein said alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm, described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate;
Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, and their weight ratio is 3:4:1:2:10, and wherein, described microcapsule red phosphorus median size is 15 μm, and described particle size carbon black is 10nm;
Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2, wherein, and described nano silicon purity >99%, median size 10nm, described whisker can be one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker;
Anti-dripping agent is tetrafluoroethylene;
Antioxidant is 1010;
Char-forming agent is novolac epoxy and OMMT, and form by weight 5:1 blending and modifying, described novolac epoxy epoxy equivalent (weight) is 210, and described OMMT is 400 orders.
Preparation process is:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mixed in (6) and ABS are carried out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
Embodiment 2:
ABS matrix 60 parts;
Main fire-retardant matrix 15 parts;
Synergist matrix 6 parts;
Strengthen matrix 12 parts;
Char-forming agent 3 parts;
Anti-dripping agent 1 part;
Antioxidant 1 part;
1 part, paraffin and look female 1 part.
Wherein:
ABS base rubber content is 40%;
Main fire-retardant matrix is by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1.5:10, wherein said alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm, described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate;
Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, and their weight ratio is 3:4:1:2:10, and wherein, described microcapsule red phosphorus median size is 15 μm, and described particle size carbon black is 10nm;
Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2, wherein, and described nano silicon purity >99%, median size 10nm, described whisker can be one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker;
Anti-dripping agent is tetrafluoroethylene;
Antioxidant is 1010;
Char-forming agent is novolac epoxy and OMMT, and form by weight 5:1 blending and modifying, described novolac epoxy epoxy equivalent (weight) is 210, and described OMMT is 400 orders.
Preparation process is:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS base-material according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mix (6) and ABS base-material carry out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
Embodiment 3:
ABS matrix 65 parts;
Main fire-retardant matrix 12 parts;
Synergist matrix 6 parts;
Strengthen matrix 11 parts;
Char-forming agent 2 parts;
Anti-dripping agent 1 part;
Antioxidant 1 part;
1 part, paraffin and look female 1 part.
Wherein:
ABS base rubber content is 40%;
Main fire-retardant matrix is by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1.5:10, wherein said alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm, described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate;
Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, and their weight ratio is 3:4:1:2:10, and wherein, described microcapsule red phosphorus median size is 15 μm, and described particle size carbon black is 10nm;
Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2, wherein, and described nano silicon purity >99%, median size 10nm, described whisker can be one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker;
Anti-dripping agent is tetrafluoroethylene;
Antioxidant is 1010;
Char-forming agent is novolac epoxy and OMMT, and form by weight 5:1 blending and modifying, described novolac epoxy epoxy equivalent (weight) is 210, and described OMMT is 400 orders.
Preparation process is:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS base-material according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mixed in (6) and ABS are carried out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
Embodiment 4:
ABS matrix 70 parts;
Main fire-retardant matrix 10 parts;
Synergist matrix 5 parts;
Strengthen matrix 10 parts;
Char-forming agent 1 part;
Anti-dripping agent 1 part;
Antioxidant 1 part;
1 part, paraffin and look female 1 part.
Wherein:
ABS base rubber content is 40%;
Main fire-retardant matrix is by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1.5:10, wherein said alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm, described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate;
Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, and their weight ratio is 3:4:1:2:10, and wherein, described microcapsule red phosphorus median size is 15 μm, and described particle size carbon black is 10nm;
Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2, wherein, and described nano silicon purity >99%, median size 10nm, described whisker can be one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker;
Anti-dripping agent is tetrafluoroethylene;
Antioxidant is 1010;
Char-forming agent is novolac epoxy and OMMT, and form by weight 5:1 blending and modifying, described novolac epoxy epoxy equivalent (weight) is 210, and described OMMT is 400 orders.
Preparation process is:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS base-material according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mixed in (6) and ABS base-material are carried out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
Table 1 is obtained flame-retardant reinforced ABS composite material performance test data
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 prerequisite not departing from the inventive method; can also make some improvement and supplement, these improve and supplement and also should be considered as protection scope of the present invention.
Claims (9)
1. a halogen-free flame-retardant enhancement type ABS, it is characterized in that: be made up of ABS matrix, main fire-retardant matrix, synergistic matrix, enhancing matrix, anti-dripping agent, antioxidant, char-forming agent, paraffin and Masterbatch, the parts by weight of each component are followed successively by: ABS matrix 55-70 part, main fire-retardant matrix 10-20 part, synergist matrix 5-8 part, enhancing matrix 10-15 part, char-forming agent 1-5 part, anti-dripping agent 1-2 part, antioxidant 1-2 part, paraffin 1-2 part and look female 1-2 part; Wherein, lead fire-retardant matrix by fire retardant alkyl hypophosphite, aromatic diphosphate, Resorcinol-bis-(xylenylphosphate) polycondensate and ABS resin composition, their weight ratio is 3:2:1-1.5:10; Synergistic matrix is made up of trimerization ammonia cyanuric acid, tricyanic acid poly-phosphate, microcapsule red phosphorus, carbon black and ABS resin, and their weight ratio is 3:4:0.5-1:2:10; Strengthen matrix to be made up of nano silicon and whisker, their weight ratio is 1:2; Char-forming agent is made up of novolac epoxy and OMMT, by weight 5:1; Anti-dripping agent is tetrafluoroethylene, and antioxidant is 1010 or 168 or B219.
2. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described ABS base rubber content is 40%.
3. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described alkyl hypophosphite is two base hypo-aluminum orthophosphates, and phosphorus content is 23%-24%, and particle diameter is 15 μm.
4. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described aromatic diphosphate is four-(2,6-xylyl) resorcinol diphosphate.
5. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, it is characterized in that: described microcapsule red phosphorus median size is 15 μm, particle size carbon black is 10nm.
6. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described nano silicon purity >99%, median size 10nm.
7. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described whisker is one or more in potassium titanate crystal whisker, silicon carbide whisker and aluminium borate whisker.
8. a kind of halogen-free flame-retardant enhancement type ABS according to claim 1, is characterized in that: described novolac epoxy, and epoxy equivalent (weight) is 210, OMMT particle diameter is 400 orders.
9. prepare the method for halogen-free flame-retardant enhancement type ABS as claimed in claim 1, it is characterized in that, comprise the following steps:
(1). in flask, add appropriate novolac epoxy and OMMT according to the above ratio, heating in water bath to 70 DEG C, stir 30min, rotating speed 300r/min, blending and modifying obtains char-forming agent, for subsequent use;
(2). mixed by main flame retardant according to aforementioned proportion high-speed mixer, rotating speed is 1100r/min, and mixing time 5 ~ 10min is for subsequent use;
(3). be 1:5 by the main flame retardant in (2) and ABS base-material according to weight ratio, above-mentioned pre-composition is dropped into twin screw extruder and carries out extruding pelletization, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 200 DEG C, three DEG CHe tetra-district of district 195, engine speed 1000r/min, feeding rotating speed 400r/min, extruding pelletization prepares main fire-retardant matrix pellet;
(4). mixed by synergist according to aforementioned proportion high-speed mixer, rotating speed is 900r/min, and mixing time 5 ~ 10min is for subsequent use;
(5). be that 1:6 adds twin screw extruder and carries out extruding pelletization by the synergist in (4) and ABS base-material according to weight ratio, twin-screw extrusion machine barrel temperature is 180 DEG C, a district, 195 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1050r/min, feeding rotating speed 350r/min, synergistic matrix pellet prepared by extruding pelletization, for subsequent use;
(6). reinforcement mixed according to aforementioned proportion high-speed mixer, rotating speed is 1000r/min, and mixing time 5 ~ 10min is for subsequent use;
(7). the reinforcement mixed in (6) and ABS base-material are carried out extruding pelletization according to weight ratio 1:3 twin screw extruder, twin-screw extrusion machine barrel temperature is 175 DEG C, a district, 190 DEG C, 2nd district, 205 DEG C, three DEG CHe tetra-district of district 200, engine speed 1000r/min, feeding rotating speed 350r/min, extruding pelletization is prepared and is strengthened matrix pellet, for subsequent use;
(8). pellet prepared by (3), (5) and (7) is placed in baking oven, 80 DEG C, dry 2.5h;
(9). proportionally pellet, char-forming agent, antioxidant, anti-dripping agent, char-forming agent and paraffin that (8) dry are added injection moulding machine, wherein in injection moulding machine machine barrel, temperature is: 180 DEG C, a district, 205 DEG C, two DEG CHe tri-district of district 195, melt temperature in injection moulding machine is that the nozzle injection of 200 DEG C is in the die cavity of mould, die temperature is 60 ~ 80 DEG C, melt in die cavity is pressurize 6s under the pressure of 30MPa, after cooling, obtained halogen-free flame-retardant enhancement type ABS.
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