CN102181123A - Halogen-free intumescent flame-retardant ABS (acrylonitrile-butadiene-styrene) material and preparation method thereof - Google Patents

Abstract

The invention discloses a halogen-free intumescent flame-retardant ABS (acrylonitrile-butadiene-styrene) material. The material is composed of the following raw materials in parts by mass: 55-70 parts of ABS, 20-25 parts of flame retardant, 10-20 parts of toughening agent, 2-5 parts of compatilizer, 0.3-0.6 part of antioxidant and 0.2-0.5 part of processing aid. The preparation method of the halogen-free intumescent flame-retardant ABS material comprises the following steps: (1) weighing and evenly mixing the raw materials; and (2) placing the obtained mixture in a double screw extruder for melting and extrusion, drawing into strips, cooling and granulating. The halogen-free flame-retardant ABS material has the advantages of good flame retardance up to grade V0 and better impact property, thus further widening the use range.

Description

A kind of halogen-free expansion type flame-proof ABS material and preparation method thereof

Technical field

The present invention relates to a kind of halogen-free expansion type flame-proof ABS material and preparation method thereof.

Background technology

ABS resin is a kind of thermoplastics of excellent property, has high impulse strength, and thermotolerance and dimensional stability are because its various advantages that has is widely used in industrial spare and accessory parts, shells of electronics and driving member, and other field.The ABS resin has three-phase structure, does not contain Sauerstoffatom in the group, is difficult for being dehydrated into charcoal, and the flame retardant resistance of itself is extremely low, and oxygen index only is about 18, and the vertical combustion experiment can't reach UL94 V0 standard.Most halogenated flame retardants all has excellent thermostability and heat aging performance, good cost performance, and halogen-antimony synergistic is fire-retardant, and to relate to condensed phase fire-retardant and gas phase is fire-retardant, and ABS resin is had very high flame retarding efficiency, is the fire retardant of present main flow.US4880862, US3965214, CN101497735, CN101704983A, CN1962751, CN1765985 all adopt Sb ₂O ₃And halogen flame.But halogenated flame retardant more specifically, is halogen-antimony flame retardant systems, is certain to produce corrodibility and toxic substances such as dioxan, Dioxins when burning or hot tearing, can cause very big harm to environment and human health.European Union issued WEEE and RoSH instruction in 2002, and material is fire-retardant towards Halogen, the trend development of low toxicity, and the exploitation halogen-free flame retardant ABS just seems extremely urgent.

CN1616545 discloses the composite flame retardant system of phosphoric acid ester, polyphenylene oxide, Resins, epoxy, but phosphoric acid ester fire retardant fusing point is low, and stickiness is big, poor in processability.CN1908062 selects for use magnesium salt whisker and acicular wollastonite whisker fire-retardant.Inorganic combustion inhibitor, though can not discharge toxic gas in the fire-retardant process, for ABS, addition is too much, grievous injury the mechanical property of ABS, greatly influenced the range of application of ABS.Expanding fire retardant is a kind of halogen-free environment-friendly flame-proof agent of studying recently, and it belongs to the composite inorganic system of N-P, wide material sources in essence.Traditional expansion type flame retardant (APP/PER/MA) is not high to the ABS flame retarding efficiency, and addition is more, and is poor with the consistency of ABS system, bad dispersibility, and water absorbability is strong.Above-mentioned several halogen-free flame retardants all destroys bigger to the impact property of ABS resin, greatly limited the range of application of ABS.

Summary of the invention

The purpose of this invention is to provide a kind of halogen-free expansion type flame-proof ABS material and preparation method thereof.

The technical solution used in the present invention is:

A kind of halogen-free expansion type flame-proof ABS material, its raw material by following mass parts is formed: the compatilizer of the fire retardant of the ABS of 55-70 mass parts, 20-25 mass parts, the toughner of 10-20 mass parts, 2-5 mass parts, the oxidation inhibitor of 0.3-0.6 mass parts, the processing aid of 0.2-0.5 mass parts.

Described fire retardant is the mixture of phosphinates and melamine salt, and wherein, the quality percentage composition of phosphinates is 70-90%.

The structural formula of described phosphinates such as formula I or (II):

Wherein, the R of phosphinates ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉, R ₁₀Be respectively a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the phenyl, N ²⁺Be Zn ²⁺, Ca ²⁺, Mg ²⁺In a kind of, M ³⁺Be Al ³⁺

Described melamine salt is at least a in melamine cyanurate (MCA), tetra-sodium two trimeric cyanamides (DMPY), ortho-phosphoric acid trimeric cyanamide (MMP), polyphosphoric acid melamine (MPP), ortho-phosphoric acid two trimeric cyanamides (DMP).

Described toughner is at least a in nylon elastomer (TPEA), methyl methacrylate-butadiene-styrene terpolymer (MBS), thermoplastic polyurethane (TPU), thermoplastic polyester elastomer (TPEE), ethylene methyl acrylate carbonyl multipolymer (EMA), the ethylene-vinyl acetate copolymer (EVA).

Described compatilizer is at least a among SEBS-g-MAH, ABS-g-MAH, the SMA.

Described oxidation inhibitor is 1076,1010,300,245,1035,1222,168, at least a among the BHT.

Described processing aid is polyethylene wax, calcium stearate and N, at least a in the N-ethylene bis stearamide (EBS).

A kind of halogen-free expansion type flame-proof ABS preparation methods may further comprise the steps:

1) takes by weighing raw material, raw material is mixed;

2) mixture is placed twin screw extruder melt extrudes, tie rod, cooling, pelletizing.

The invention has the beneficial effects as follows: halogen-free flame retardant ABS material of the present invention, flame retardant properties reaches the V0 rank, has impact property preferably simultaneously, has further widened its use range.

Embodiment

A kind of halogen-free expansion type flame-proof ABS preparation methods is characterized in that: may further comprise the steps:

1) takes by weighing raw material, place high-speed mixer to mix raw material;

2) mixture is placed twin screw extruder melt extrudes, tie rod, cooling, pelletizing.

Wherein, the length-to-diameter ratio of screw rod is 30:1 ~ 75:1, and the temperature that melt extrudes is 190-220 ℃.

In the raw material, fire retardant is the mixture of phosphinates and melamine salt, and wherein, the quality percentage composition of phosphinates is 70-90%, and preferred, the quality percentage composition of phosphinates is 75%.

Below in conjunction with embodiment prescription of the present invention is described further:

Embodiment 1:

Shown in the raw material table 1 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 2:

Shown in the raw material table 2 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 3:

Shown in the raw material table 3 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 4:

Shown in the raw material table 4 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 5:

Shown in the raw material table 5 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 6:

Shown in the raw material table 6 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 7:

Shown in the raw material table 7 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 8:

Shown in the raw material table 8 composed as follows of halogen-free expansion type flame-proof ABS material:

Embodiment 1-8 is injected into test bars respectively, tests its mechanical property and flame retardant properties respectively, as shown in table 9 below:

As can be seen, product of the present invention has flame retardant properties, impact resistance and tensile property preferably, applied range.

Claims (9)

1. halogen-free expansion type flame-proof ABS material, it is characterized in that: its raw material by following mass parts is formed: the compatilizer of the fire retardant of the ABS of 55-70 mass parts, 20-25 mass parts, the toughner of 10-20 mass parts, 2-5 mass parts, the oxidation inhibitor of 0.3-0.6 mass parts, the processing aid of 0.2-0.5 mass parts.

2. a kind of halogen-free expansion type flame-proof ABS material according to claim 1, it is characterized in that: described fire retardant is the mixture of phosphinates and melamine salt, wherein, the quality percentage composition of phosphinates is 70-90%.

3. a kind of halogen-free expansion type flame-proof ABS material of stating according to claim 2 is characterized in that: the structural formula of described phosphinates such as formula I or (II):

Wherein, the R of phosphinates ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉, R ₁₀Be respectively a kind of in hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-pentyl, the phenyl, N ²⁺Be Zn ²⁺, Ca ²⁺, Mg ²⁺In a kind of, M ³⁺Be Al ³⁺

4. a kind of halogen-free expansion type flame-proof ABS material according to claim 2 is characterized in that: described melamine salt is at least a in melamine cyanurate (MCA), tetra-sodium two trimeric cyanamides (DMPY), ortho-phosphoric acid trimeric cyanamide (MMP), polyphosphoric acid melamine (MPP), ortho-phosphoric acid two trimeric cyanamides (DMP).

5. a kind of halogen-free expansion type flame-proof ABS material according to claim 1 is characterized in that: described toughner is at least a in nylon elastomer (TPEA), methyl methacrylate-butadiene-styrene terpolymer (MBS), thermoplastic polyurethane (TPU), thermoplastic polyester elastomer (TPEE), ethylene methyl acrylate carbonyl multipolymer (EMA), the ethylene-vinyl acetate copolymer (EVA).

6. a kind of halogen-free expansion type flame-proof ABS material according to claim 1 is characterized in that: described compatilizer is at least a among SEBS-g-MAH, ABS-g-MAH, the SMA.

7. a kind of halogen-free expansion type flame-proof ABS material according to claim 1 is characterized in that: described oxidation inhibitor is 1076,1010,300,245,1035,1222,168, at least a among the BHT.

8. a kind of halogen-free expansion type flame-proof ABS material according to claim 1, it is characterized in that: described processing aid is polyethylene wax, calcium stearate and N, at least a in the N-ethylene bis stearamide (EBS).

9. halogen-free expansion type flame-proof ABS preparation methods is characterized in that: may further comprise the steps:

1) takes by weighing raw material, raw material is mixed;

2) mixture is placed twin screw extruder melt extrudes, tie rod, cooling, pelletizing.