CN101704983A - High-performance flame-resistant ABS resin and preparation method thereof - Google Patents

Abstract

The invention provides a high-performance flame-resistant ABS resin and a preparation method thereof, wherein the formula proportion of the resin is as follows (by weight percent): 40 to 60 percent of ABS resin, 10 to 15 percent of nanoscale kaolin, 10 to 15 percent of bromine-nitrogen type flame retardant, 10 to 13 percent of antimony trioxide, 9.4 to 16 percent of compound flexibilizer, and 0.6 to 1.0 percent of antioxidant 1010. The performance of the high-performance flame-resistant ABS resin prepared according to the formula meets the environmental protection requirement of European Union, namely, fireproof performance 1/12'' reaches requirement of UL94V-0, thus being widely applied to occasions having higher requirement on the flame-resistant performance of material, such as domestic appliance, office equipment and instruments and apparatuses and the like, and having simple manufacturing technology, low cost, and good flame resistance and physical property.

Description

A kind of high-performance flame-resistant ABS resin and preparation method thereof

Technical field

The present invention relates to chemical technology field, particularly, relate to a kind of high-performance flame-resistant ABS resin and preparation method thereof.

Background technology

The terpolymer that resin is fine by propylene for ABS (Acrylonitrile Butadiene Styrene), divinyl and vinylbenzene are formed.ABS resin is because of showing three kinds of synergisticing performances between the component, so have the surface hardness height, tough and tensile, low-temperature impact resistance good, anti-creep shape is good, dimensional stability is good, molding shrinkage is little, the good excellent properties that waits of processing characteristics, by extensive household electrical appliance, office appliance, electron device, fields such as automotive industry.

Yet the flame retardant properties of ABS resin own is extremely low, and its oxygen index is 18.3～20 only, belongs to inflammable material, becomes the obstacle that it is applied in some field, particularly to the fire-retardant field that requirement is arranged.In order to solve this obstacle, people have carried out a large amount of research, and obtain certain effect.Human siloxanes such as nineteen fifty-five American Phreaner are made fire retardant, have prepared flame-proof ABS, have opened the gate of flame-proof ABS research.People's success such as HINDERSINN sixties in 20th century flame-retardant modified to ABS with halogenide greatly promoted the development of flame-proof ABS.The eighties to the nineties in 20th century, the application development of flame-proof ABS reached the period of great prosperity, in this phase application the patent of a large amount of flame-proof ABSs.Now, flame-proof ABS has moved towards the new stage that the performance direction develops, and it is used more and more widely, and is also more and more higher to the ABS performance demands.As, flame-proof ABS requires to meet to reach the 5VA requirement when European Union environmental protection requirement, fire resistance 1/12 " reach the UL94V-0 requirement, 1/10 ".

At present, the flame-retardant modified method of Chang Yong ABS is composite by a certain percentage with brominated flame retardant and antimonous oxide.But after fireproofing agent total addition level to 20%, the ABS rerum natura is had a strong impact on, and acutely descends as resistance to impact shock, must dose a certain amount of toughner again and carry out toughening modifying to recover the original physicals of material.Want to reach fire resistance 1/12 and reach the 5VA requirement when " reaching the UL94V-0 requirement, 1/10 ", must in the ABS material, add a large amount of fireproofing agent and toughner, Zhi Bei anti-flaming ABS material cost height so not only, poor properties lacks competitive edge with like product.

Summary of the invention

One of purpose of the present invention is to solve the deficiencies in the prior art, a kind of high-performance flame-resistant ABS resin is provided, adopt nano-kaoline to mix, work in coordination with flame-retardant modifiedly, make its fire resistance 1/12 and reach the 5VA requirement when " reaching the UL94V-0 requirement; 1/10 " ABS with bromine nitrogen based flame retardant and antimonous oxide, the rerum natura height, and it is simple to have manufacturing process, low cost and other advantages, and it is required with application to satisfy large-scale industrialization production, and the flame-proof ABS product of high performance-price ratio is provided to society.

Two of purpose of the present invention provides the preparation method of described high-performance flame-resistant ABS resin

Technical scheme of the present invention is as follows: a kind of high-performance flame-resistant ABS resin, the formulation ratio of this resin (weight percent) is: ABS resin 40～60%, nano-kaoline 10～15%, bromine nitrogen based flame retardant 10～15%, antimonous oxide 10～13%, composite toughing agent 9.4～16%, antioxidant 0.6～1.0%.

The formulation ratio of this resin (weight percent) is: ABS resin 58%, nano-kaoline 10%, bromine nitrogen based flame retardant 12%, antimonous oxide 10%, composite toughing agent 9%, antioxidant 1.0%.

Described nano-kaoline contains silicon-dioxide, aluminium sesquioxide, ferric oxide, magnesium oxide, tellurium dioxide etc. the fire prevention functional component.

Described composite toughing agent is the mixture of styrene-butadiene-styrene block copolymer (SBS) and acrylonitrile styrene resin (AS) (AS).

Described antioxidant is the mixture of phenol antioxidant 1010 and phosphoric acid ester antioxygen thinner agent 168.

The preparation method of described high-performance flame-resistant ABS resin comprises the steps:

(1) get nano-kaoline, high speed mixer is put in oven dry, heats, and stirs, and when temperature is raised to 120 ℃, adds the chelating type additives for plastics, carries out the affinity modification;

(2) with the nano-kaoline after the affine modification of step (1) gained, ABS resin, bromine nitrogen based flame retardant, antimonous oxide, composite toughing agent and antioxidant are put into stirrer and are stirred;

(3) with the mixed raw materials melt of step (2) gained, pressure is 15～30MPa, and temperature is 175 ℃～230 ℃;

(4) raw material after step (3) the gained fusion is extruded pelletizing, packing from stirrer.

Flame-retardant modified common employing bromine nitrogen based flame retardant of ABS and the composite by a certain percentage method of antimonous oxide, but when the fireproofing agent total addition level behind certain proportion, material property descends significantly, wants to keep material property, must add a certain amount of toughner again and carry out toughening modifying.And, want to meet the European Union environmental protection requirement, reach the 5VA requirement when promptly fire resistance 1/12 " reaching the UL94V-0 requirement; 1/10 ", must increase more fireproofing agent and toughner, like this, material property after the modification is poor, and modification cost height lacks competitive edge with international like product.It is composite that the present invention adopts nano-kaoline and bromine nitrogen class fireproofing agent to carry out, collaborative flame-retardant modified to HIPS with tellurium dioxide again, both can reduce the consumption of bromine nitrogen based flame retardant and antimonous oxide, reduces material cost again, improves material property.Simultaneously, adopt styrene-butadiene-styrene block copolymer (styrene-butadiene block copolymer, SBS) and acrylonitrile styrene resin (AS) (acrylonitrile-styrene resin, AS) mixture is that the composite toughening system comprehensively improves toughness of material, adopts phenolic antioxidant 1010 and phosphoric acid ester oxidation inhibitor 168 composite raising material ageing resistances.

Adopt the weighting agent of nano-kaoline in the present invention as fire-resistant synergistic, during burning, nano kaoline forms a kind of carbonized silicate structure at composite material surface, the unburned material in the inside has been played heat insulation and isolating effect, make the labile gas that is heated be difficult to select, reduced the diffusion of volatilizable product, reduced the mass loss rate of matrix material, thereby improved flame retardant properties, on the other hand, because the specific surface area of clay layer is bigger, homodisperse lamella has stopped the diffusion of gas molecule in matrix material, its movement path is prolonged greatly, further reduced the diffusion of volatilizable product, improved flame retardant properties.

In addition, in preparation technology, nano-kaoline is carried out affine modification.The activator that adopts in the affine modifying process has multiple different properties functional group, a part functional group can with reactive organic molecule, another part functional group can form stable hydrogen bond with the kaolin surface, form firm bonding, between nano material and resin matrix, form an interfacial layer, interfacial layer can transmit stress, thereby strengthened bond strength between nano material and the resin, improved performance of composites, can also prevent simultaneously not with other medium to contacting permeation, improve interfacial state, helped the ageing-resistant of goods, proof stress and electrical insulation capability.Significantly improve physical and chemical performance.Do not have the Nano filling of modification in plastic material, to be difficult to keep due nanometer effect, not only influence physicals, and influence fire resistance.

Use nano-kaoline to be also that as the advantage of the weighting agent of fire-resistant synergistic nano-kaoline derives from kaoline deposit, impure few, the crystal layer surface has neutral charge, and purity and whiteness height can be used for light color or white plastic and rubber industry.

Advantage of the present invention is: after (1) nano-kaoline and bromine nitrogen based flame retardant and antimonous oxide are composite, cooperative flame retardant ABS, both can reduce the consumption of bromine nitrogen class fireproofing agent and antimonous oxide, reduce cost again, improve material property. (2) carry out the affinity modification with nanometer fireproof level kaolin, there is not the Nano filling of modification in plastic material, to be difficult to keep due nanometer effect, not only influence physicals, and influence fire resistance, kaolin after the affine modification is little to the influence of ABS rerum natura, and smooth surface. the ABS composite property of (3) the present invention preparation meets the European Union environmental protection requirement, being fire resistance 1/12 reaches the 5VA requirement when " reaching the UL94V-0 requirement, 1/10 ", can be widely used in household electrical appliance, the occasion that office equipment and instrument etc. can have higher requirements to Flame Retardancy, its manufacturing process is simple, the working (machining) efficiency height is drawn materials conveniently, and cost is low, the product whiteness height, flame retardant resistance and rerum natura are good.

Embodiment

The preparation method is: get and contain the nano-kaoline that silicon-dioxide, aluminium sesquioxide, ferric oxide, magnesium oxide, tellurium dioxide have the fire prevention functional component, oven dry, put into high speed mixer, heat, stir, when temperature is raised to 120 ℃, add the chelating type additives for plastics, carry out the affinity modification; With nano-kaoline after the modification and ABS, bromine nitrogen based flame retardant, antimonous oxide, styrene-butadiene-styrene block copolymer, acrylonitrile styrene resin (AS), phenol antioxidant 1010 and phosphoric acid ester oxidation inhibitor 168 are put into stirrer, stir; With the mixture fusion after stirring, pressure is 15～30MPa, and temperature is 175 ℃～230 ℃, extrudes pelletizing, packing from stirrer.

Used bromine nitrogen based flame retardant is a brominated triazine in the present embodiment.

The mixture of each embodiment preparation is injection molded into the standard batten of testing usefulness by standard size, and the physicals of each embodiment is respectively by China's national standard test, and is as shown in table 1.Each Example formulations and physicals are as shown in table 2.

Table 1

Physicals	Unit	Testing method
			Density	g/cm 3	GB1033
Glossiness	％	GB/T13891
			Tensile strength	Mpa	GB/T1040
Tension fracture elongation rate	％	GB/T1040
			Flexural strength	Mpa	GB/T9341
The Izod notched Izod impact strength	KJ/m 2	GB/T1843
			Heat-drawn wire	℃	GB/T1634(45℃mpu)
Melt index	g/10min	GB/T3682(220℃/5kg)
			Incendivity		GB4609

Table 2

The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with the described structure of claim of the present invention, feature and principle change or modify, all should be included within the claim scope of the present invention.

Claims (6)

1. high-performance flame-resistant ABS resin, it is characterized in that, the formulation ratio of this resin (weight percent) is: ABS resin 40～60%, nano-kaoline 10～15%, bromine nitrogen based flame retardant 10～15%, antimonous oxide 10～13%, composite toughing agent 9.4～16%, antioxidant 0.6～1.0%.

2. high-performance flame-resistant ABS resin as claimed in claim 1 is characterized in that, the formulation ratio of this resin (weight percent) is: ABS resin 58%, nano-kaoline 10%, bromine nitrogen based flame retardant 12%, antimonous oxide 10%, composite toughing agent 9%, antioxidant 1.0%.

3. high-performance flame-resistant ABS resin as claimed in claim 1 or 2 is characterized in that described nano-kaoline contains silicon-dioxide, aluminium sesquioxide, ferric oxide, magnesium oxide and tellurium dioxide.

4. high-performance flame-resistant ABS resin as claimed in claim 1 or 2 is characterized in that, described composite toughing agent is the mixture of styrene-butadiene-styrene block copolymer and acrylonitrile styrene resin (AS).

5. high-performance flame-resistant ABS resin as claimed in claim 1 or 2 is characterized in that, described antioxidant is the mixture of phenol antioxidant 1010 and phosphoric acid ester antioxygen thinner agent 168.

6. the preparation method of each described high-performance flame-resistant ABS resin of preparation claim 1～5 is characterized in that, comprises the steps:

(1) get nano-kaoline, high speed mixer is put in oven dry, heats, and stirs, and when temperature is raised to 120 ℃, adds the chelating type additives for plastics, carries out affine modification;

(2) with nano-kaoline and ABS resin after the affine modification of step (1) gained, bromine nitrogen based flame retardant, antimonous oxide, composite toughing agent and antioxidant are put into stirrer and are stirred;

(3) with the mixed raw materials melt of step (2) gained, pressure is 15～30MPa, and temperature is 175 ℃～230 ℃;

(4) raw material after step (3) the gained fusion is extruded pelletizing, packing from stirrer.