CN104371257A - Multifunctional ABS composite material - Google Patents

Abstract

The invention provides a multifunctional ABS composite material, which is characterized being composed of the following components in parts by weight: 60 to 90 parts of ABS resin, 10 parts of ABS-g-MAH, 5 to 10 parts of alkali-free chopped glass fiber, 0.5 to 1.0 part of ferroferric oxide, 2 to 3 parts of composite carbon black, 0.5 to 0.8 part of lubricant, 5 to 10 parts of phosphorus flame retardant, 5 to 10 parts of nitrogen flame retardant, 0.5 to 1.0 part of silicon synergist, 2 to 3 parts of antistatic agent, and 0.5 to 1.0 part of antioxidant 1010. The phosphorus flame retardant and nitrogen flame retardant or the phosphorus flame retardant and silicon synergist are used together to generate a synergetic effect so as to improve the flame retardant efficiency, moreover, the toxic gas released during the burning process is reduced, and the provided ABS composite material has the advantages of low smoke and toxicity. Furthermore, the ABS composite material has a good mechanical property and a good electromagnet shielding performance, and has the advantages of rapid heat radiation, high electromagnet shielding efficiency, long-lasting antistatic effect, high mechanical strength, and easiness for flow processing. The application range of the ABS composite material is enlarged.

Description

A kind of ABS composite material of many performances

Technical field

The invention belongs to composite processing field, be specifically related to a kind of ABS composite material of many performances.

Background technology

ABS resin is the blend of acrylonitrile-butadiene-styrene copolymer or vinyl cyanide/cinnamic multipolymer and styrene/butadiene copolymers, it is the graft copolymer of divinyl and the mixture of acrylonitritrile-styrene resin, wherein vinyl cyanide accounts for 15%-35%, divinyl accounts for 5%-30%, and vinylbenzene accounts for 40-60%.Along with the change of three kinds of component proportionss, the physical and mechanical properties of ABS resin changes thereupon.ABS resin is that a kind of intensity is high, good toughness, heat-resisting, low temperature resistant, chemical resistance corrosion, physical strength and electric property are excellent, is easy to thermoplastics type's macromolecular material of machine-shaping.The fields such as ABS is widely used in automobile, electronic apparatus, building materials, packaging, sports goods, machinery instrument industry.Along with domestic ABS resin is in the increase of the industry annual requirements such as automobile, electronic apparatus, building materials, the demand of flame-proof ABS increases year by year.

For a long time, the fire-retardant main employing of ABS be halide-containing, wherein the bromide fire retardant flame retardant effect such as decabromodiphenyl oxide, tetrabromo-bisphenol, eight bromo ether is best, particularly when them and antimonous oxide coupling, can make the flame retardant properties that ABS reaches excellent.Because difficulty combustion polymkeric substance (PVC) and chlorinatedpolyethylene (CPE) and ABS have good consistency and high chlorinity, be thus also a kind of fire retardant of ABS, and small molecules fire retardant can be reduced the mechanics of ABS is lost.But these halide-containings can produce a large amount of toxic gases in burning, the ABS that PVC, CPE are fire-retardant in addition also also exists poor heat stability, the easily shortcoming such as decomposition, difficult processing.Thus under the situation that the non-halogen cry of fire retardant material is day by day surging, domestic and international investigator starts to attempt one after another all kinds of halogen-free flame retardants is applied to ABS, to obtaining the halogen-free flame retardant ABS product of low toxicity, few cigarette, high-efficiency environment friendly green.

At present, the halogen-free flame-retardant system of ABS resin and alloy thereof comprises phosphorous, nitrogen, silicon flame-retardant system and inorganic fire-retarded system.Aluminium hydroxide and magnesium hydroxide are the two kinds of inorganic combustion inhibitors commonly used the most, because of have nontoxic, press down cigarette, the advantage such as cheap and be widely used in the flame-retardant modified of ABS, but the flame retarding efficiency of inorganic powdered filler is lower, addition reaches more than 40% and just likely reaches UL94V-0 flame retardant rating, inorganic combustion inhibitor and ABS poor compatibility in addition, high amount of inorganic filler makes the mechanical properties decrease of material in ABS resin serious, and outward appearance and processing characteristics sharply worsen.

In phosphorous flame-retardant system, triphenyl and derivative thereof are widely used in polymkeric substance because flame retarding efficiency is higher, but, when TPP is applied to ABS without the obvious fire retardation of generation.This mainly due in ABS structure without oxygen-containing functional group, when being unfavorable for that phosphonium flame retardant burns formed charing film; Be on the other hand then because the volatilization temperature of TPP is lower than the processing temperature of ABS, cause TPP and volatilize in the ABS course of processing and ooze out, the flame retardant effect of expection cannot be reached.For above-mentioned reason, the phosphorus flame retardant selecting thermostability higher and introduce the flame retarding efficiency that synergist can improve ABS effectively in phosphorus flame retardant.

By using a kind of full acrylic core-shell impact modifier in prior art, the notched Izod impact strength of fire retardation PC/ABS material effectively can be improved, to draw a kind of high tenacity flame-proof ABS matrix material.Although prior art improves shock strength and the flame retardant properties of ABS matrix material, because major part have employed bromine antimony composite flame retardant system, although can effectively prevent from use combustion phenomena occurring.But corrosive bromize hydrogen gas will be decomposited in fire-retardant process, human body and environment be formed and pollutes and be harmful to.

Along with the development of electronic industry, various household electrical appliances, electronic product such as office electrical equipment, plant and instrument etc. are popularized widely and are applied, and bring and also discharge a large amount of electromagnetic radiation easily simultaneously, endanger the health of people.Current plastic base exothermic material forms matrix material mainly through adding conducting particles in plastic substrate, in time matrix material adding voltage, it can release certain heat, but, due to the problem of conducting particles dispersiveness, the heating property of current plastic base heating matrix material is poor, also causes its mechanical property to be subject to certain impact.Produce a kind of heatable electromagnetic shielding plastic based composites significant.

Although ABS is widely used, due to the characteristic of the molecular structure performance of ABS own, make ABS in mechanical strength, as flexural strength and compressive strength poor; Accumulation of static electricity is easy to due to good insulation preformance in electric property, thus limited in electric Application Areas, as the manufacture of both having required when office machine sheets mechanism, IC chip carrier that improving intensity in ABS virgin resin performance basis gave antistatic property again.ABS matrix material how is made to have anti-electrically worth research.

Therefore ABS composite material how is made to have high-performance, high-impact, antistatic, high stability and to have heatproof combustion resistance be the technical problem to be solved in the present invention.

Summary of the invention

The invention provides a kind of ABS composite material of many performances, it is characterized in that, each component is as follows according to weight distribution ratio: ABS resin 60-90 part; ABS-g-MAH 5-10 part; Alkali-free short glass fiber 5-10 part; The ferrous 0.5-1.0 part of inclined ferrous acid; Composite carbon black 2-3 part; Lubricant 0.5-0.8 part; Phosphorus flame retardant 5-10 part; Nitrogenated flame retardant 5-10 part; Silicon system synergist 0.5-1.0 part; Static inhibitor 2-3 part; Antioxidant 1010 0.5-1.0 part.

The ABS composite material of above-mentioned a kind of many performances, is characterized in that, described lubricant is at least one in calcium stearate, Magnesium Stearate, butyl stearate, oleylamide, ethylene bis stearamide.

The ABS composite material of above-mentioned a kind of many performances, is characterized in that, described phosphorus flame retardant comprises phosphoric acid salt, poly-phosphate, any one in pyrophosphate salt.

The ABS composite material of above-mentioned a kind of many performances, is characterized in that, described nitrogenated flame retardant comprises trimeric cyanamide, melamine cyanurate, any one in Dyhard RU 100 and guanidinesalt thereof.

The ABS composite material of above-mentioned a kind of many performances, is characterized in that, described silicon system synergist is silane, dimethyl siloxane, any one in silicone resin.

The ABS composite material of above-mentioned a kind of many performances, is characterized in that, described static inhibitor is one or more in magnesium oxide, titanium oxide, stannic oxide, aluminum oxide, chromic oxide, barium oxide.

The making method of the ABS composite material of above-mentioned a kind of many performances is as follows:

(1) modified particle processed: ABS and ABS-g-MAH, alkali-free short glass fiber, partially ferrous acid ferrous iron, composite carbon black, lubricant are joined high-speed mixer batch mixing according to the ratio of weight and number of regulation, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 180-220 DEG C, normal temperature is cooled to through tank after extruding, by dicing machine granulation, again gained pellet is put into baking oven, temperature range is 80-90 DEG C, dry 3-4 hour, obtains modified ABS particle;

(2) over-all properties material processed: take quantitative phosphorus flame retardant, nitrogenated flame retardant, silicon system synergist, static inhibitor, oxidation inhibitor successively; above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine; mix; then join in twin screw extruder and extrude; extrusion temperature scope is 220-260 DEG C; extrude material strip and be cooled to normal temperature by circulating water channel, after Hairdryer drying, enter dicing machine granulation.

The beneficial effect of the invention:

The flame-retardant ABS compound material that theres is provided in the present invention adopts phosphorus system and nitrogen system synergistic flame-retardant system or phosphorus system and silicon-series five-retardant is collaborative uses, the flame retarding efficiency of halogen-free flame retardant ABS material can be improved on the one hand, promote the comprehensive mechanical property of halogen-free flame-retardant ABS compound material; And the poisonous gas discharged in minimizing combustion processes, the few poison of low cigarette.Alkali-free short glass fiber, partially ferrous acid are ferrous, adding of composite carbon black make matrix material have good mechanical property and capability of electromagnetic shielding, and heating is very fast, and electromagnetic shielding efficiency is high, easy-formation processing and recyclablely to recycle, and can meet environmental requirement.Static inhibitor makes ABS have lasting antistatic effect, good physical strength, is easy to flowing processing.The basis being added in ABS composite material high strength degree performance of ABS-g-MAH improves resistance to impact shock, the obnoxious flavour that goes out of halogen decomposition when simultaneously solving the burning that prior art exists, high material cost, and limit the problem such as use range of material.

Embodiment

embodiment 1

ABS resin 85 parts, ABS-g-MAH 5 parts, alkali-free short glass fiber 5 parts, partially ferrous 0.5 part of ferrous acid, composite carbon black 2 parts, calcium stearate 0.5 part are joined high-speed mixer batch mixing, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 180 DEG C, normal temperature is cooled to through tank after extruding, by dicing machine granulation, then gained pellet is put into baking oven, temperature range is 80 DEG C, dry 3 hours, obtain modified ABS particle; Take quantitative sodium phosphate 5 parts successively; Trimeric cyanamide 5 parts; 1.0 parts, silane; 2 parts, magnesium oxide; Antioxidant 1010 0.5 part; above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine; mix; then join in twin screw extruder and extrude; extrusion temperature scope is 220 DEG C; extrude material strip and be cooled to normal temperature by circulating water channel, after Hairdryer drying, enter dicing machine granulation.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 25.7%, UL94 vertical combustion rank is V-0.

embodiment 2

ABS resin 85 parts, ABS-g-MAH 5 parts, alkali-free short glass fiber 5 parts, partially ferrous 0.5 part of ferrous acid, composite carbon black 2 parts, Magnesium Stearate 0.5 part are joined high-speed mixer batch mixing, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 200 DEG C, normal temperature is cooled to through tank after extruding, by dicing machine granulation, then gained pellet is put into baking oven, temperature range is 85 DEG C, dry 3 hours, obtain modified ABS particle; Take quantitative sodium polyphosphate 5 parts successively; Trimeric cyanamide cyanogen urea acid 5 parts, sodium; Dimethyl siloxane 1.0 parts; 2 parts, magnesium oxide; Antioxidant 1010 0.5 part; above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine; mix; then join in twin screw extruder and extrude; extrusion temperature scope is 240 DEG C; extrude material strip and be cooled to normal temperature by circulating water channel, after Hairdryer drying, enter dicing machine granulation.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 25.1%, UL94 vertical combustion rank is V-0.

embodiment 3

aBS resin 85 parts, ABS-g-MAH 5 parts, alkali-free short glass fiber 5 parts, partially ferrous 0.5 part of ferrous acid, composite carbon black 2 parts, butyl stearate 0.5 part are joined high-speed mixer batch mixing, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 220 DEG C, normal temperature is cooled to through tank after extruding, by dicing machine granulation, then gained pellet is put into baking oven, temperature range is 90 DEG C, dry 4 hours, obtain modified ABS particle; Take quantitative trisodium phosphate 5 parts successively; Dyhard RU 100 5 parts; Silicone resin 1.0 parts; 2 parts, magnesium oxide; Antioxidant 1010 0.5 part; above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine; mix; then join in twin screw extruder and extrude; extrusion temperature scope is 260 DEG C; extrude material strip and be cooled to normal temperature by circulating water channel, after Hairdryer drying, enter dicing machine granulation.The LOI of the ABS material of the phosphorus system cooperative flame retardant of gained is 25.4%, UL94 vertical combustion rank is V-0.

In the ABS composite material of a kind of many performances of the present invention, each component and parts by weight thereof are in table 1, and corresponding physicals is in table 2.The ABS composite material of a kind of many performances prepared by embodiment is injection molded into the standard batten of test by standard size, its physicals is respectively by China's national standard and U.S. UL standard testing.Wherein ABS resin is German BASF GP22.

Tensile strength GB1040

Elongation at break GB1040

Izod notched Izod impact strength GB1843

Flexural strength GB9341

Incendivity UL94

LOI GB/T 2406-93

the concrete formula of phosphorus system synergistic flame-proof ABS corresponding in table 1 reference examples and embodiment

Sample	Embodiment 1	Embodiment 2	Embodiment 3	Reference examples
					ABS resin (part)	85	85	85	99.5
ABS-g-MAH (part)	5	5	5	0
					Inclined ferrous acid is ferrous	0.5	0.5	0.5
Composite carbon black	2	2	2
					Alkali-free short glass fiber	5	5	5
Phosphoric acid salt	5	5	5
					Poly-phosphate
Pyrophosphate salt
					Trimeric cyanamide	5	5	5
Melamine cyanurate
					Dyhard RU 100
Silane	1.0	1.0	1.0
					Dimethyl siloxane
Silicone resin
					Calcium stearate	0.5	0.5	0.5
Magnesium Stearate
					Butyl stearate
Static inhibitor	0.5	0.5	0.5
					Antioxidant 1010	0.5	0.5	0.5	0.5

the mechanical property of table 2 embodiment flame-proof ABS and reference examples ABS sample and flame retardant properties

Performance	Embodiment 1	Embodiment 2	Embodiment 3	Reference examples
					Tensile strength/MPa	40.6	38.7	38. 5	44.3
Tensile modulus/GPa	2.15	2.52	2.42	27
					Elongation/%	6	5	5	7
Notched Izod impact strength/KJ/m 2	4.4	4.3	4.4	8.4
					Flexural strength/MPa	63.4	62.4	61.2	65.2
Modulus in flexure/GPa	45	4.22	45	4.12
					Flame retardant rating/3.2mm	V-0	V-0	V-0	NR
Oxygen index (LOI)/%	25.7	25.1	25.4	18

Claims (7)

1. an ABS composite material for performance more than, is characterized in that, each component is as follows according to weight distribution ratio:

aBS resin 60-90 part;

aBS-g-MAH 5-10 part;

alkali-free short glass fiber 5-10 part;

part;

composite carbon black 2-3 part;

part;

phosphorus flame retardant 5-10 part;

nitrogenated flame retardant 5-10 part;

part;

static inhibitor 2-3 part;

part.

2. the ABS composite material of a kind of many performances according to claim 1, is characterized in that, described lubricant is at least one in calcium stearate, Magnesium Stearate, butyl stearate, oleylamide, ethylene bis stearamide.

3. the ABS composite material of a kind of many performances according to claim 1, it is characterized in that, described phosphorus flame retardant comprises phosphoric acid salt, poly-phosphate, any one in pyrophosphate salt.

4. the ABS composite material of a kind of many performances according to claim 1, it is characterized in that, described nitrogenated flame retardant comprises trimeric cyanamide, melamine cyanurate, any one in Dyhard RU 100 and guanidinesalt thereof.

5. the ABS composite material of a kind of many performances according to claim 1, is characterized in that, described silicon system synergist is silane, dimethyl siloxane, any one in silicone resin.

6. the ABS composite material of a kind of many performances according to claim 1, is characterized in that, described static inhibitor is one or more in magnesium oxide, titanium oxide, stannic oxide, aluminum oxide, chromic oxide, barium oxide.

7. the making method of the ABS composite material of a kind of many performances according to claim 1 is as follows:

(1) modified particle processed: ABS and ABS-g-MAH, alkali-free short glass fiber, partially ferrous acid ferrous iron, composite carbon black, lubricant are joined high-speed mixer batch mixing according to the ratio of weight and number of regulation, join melt blending in twin screw extruder after mud conjunction evenly to extrude, and to control extruder temperature scope be 180-220 DEG C, normal temperature is cooled to through tank after extruding, by dicing machine granulation, again gained pellet is put into baking oven, temperature range is 80-90 DEG C, dry 3-4 hour, obtains modified ABS particle;

(2) over-all properties material processed: take quantitative phosphorus flame retardant, nitrogenated flame retardant, silicon system synergist, static inhibitor, oxidation inhibitor successively; above component and the ABS particle that adds conductive material are joined in high speed mixing smelting machine; mix; then join in twin screw extruder and extrude; extrusion temperature scope is 220-260 DEG C; extrude material strip and be cooled to normal temperature by circulating water channel, after Hairdryer drying, enter dicing machine granulation.