阅读说明：本技术 一种无锑阻燃abs/cpe合金材料及其制备方法 (Antimony-free flame-retardant ABS/CPE alloy material and preparation method thereof ) 是由 初汉顺 于 2020-07-28 设计创作，主要内容包括：本发明属于复合材料技术领域,具体涉及一种无锑阻燃ABS/CPE合金材料及其制备方法,包括如下重量份的原料组分：ABS树脂60-80％；CPE 6-20％；溴系阻燃剂10-20％；成碳阻燃协效剂3-6％,硅硼系阻燃协效剂2-4％,锑增效母粒1-2％,高岭土2-4％；水滑石1-2％；抗氧剂0.2-0.5％；润滑剂0.5-1.0％；抗滴落剂0.2-0.3％。该材料通过添加CPE与锑粉替代物复配,实现了无锑化,消除了阻燃ABS材料对锑元素的过度依赖,对整个产业的稳定性以及抗风险能力的提升,具有重要意义。(The invention belongs to the technical field of composite materials, and particularly relates to an antimony-free flame-retardant ABS/CPE alloy material and a preparation method thereof, wherein the antimony-free flame-retardant ABS/CPE alloy material comprises the following raw material components in parts by weight: 60-80% of ABS resin; 6-20% of CPE; 10-20% of brominated flame retardant; 3-6% of carbon-forming flame-retardant synergist, 2-4% of silicon-boron flame-retardant synergist, 1-2% of antimony synergistic master batch and 2-4% of kaolin; 1-2% of hydrotalcite; 0.2 to 0.5 percent of antioxidant; 0.5 to 1.0 percent of lubricant; 0.2 to 0.3 percent of anti-dripping agent. The material is compounded by adding CPE and antimony powder substitutes, so that antimonization is avoided, excessive dependence of the flame-retardant ABS material on antimony elements is eliminated, and the flame-retardant ABS material has important significance in improving the stability and risk resistance of the whole industry.)

1. An antimony-free flame-retardant ABS/CPE alloy material is characterized by comprising the following raw material components in parts by weight:

60-80% of ABS resin; 6-20% of CPE; 10-20% of brominated flame retardant; 3-6% of carbon-forming flame-retardant synergist, 2-4% of silicon-boron flame-retardant synergist, 1-2% of antimony synergistic master batch and 2-4% of kaolin; 1-2% of hydrotalcite; 0.2 to 0.5 percent of antioxidant; 0.5 to 1.0 percent of lubricant; 0.2 to 0.3 percent of anti-dripping agent.

2. The antimony-free flame retardant ABS/CPE alloy material according to claim 1, characterized in that the ABS resin is a terpolymer synthesized from acrylonitrile, butadiene and styrene, comprising one or more combinations of trademarks AE8000 AE8200 AG10NPAG10 AP12A 115A 1, LGHF 380 HF390 HI100H HI121H, Jilin petrochemical 0215H.

3. The antimony-free flame retardant ABS/CPE alloy material according to claim 1, wherein the CPE is chlorinated polyethylene and is white powder in appearance, including one or more combinations of the designation 135A 3135713052362135.

4. The antimony-free flame retardant ABS/CPE alloy material according to claim 1, characterized in that the brominated flame retardant comprises decabromodiphenylethane, hexabromocyclododecane, tetrabromobisphenol A or bromotriazine.

5. The antimony-free flame-retardant ABS/CPE alloy material as claimed in claim 1, wherein the silicon-boron flame-retardant synergist is a composite product composed of silicon, tin, boron and fluorine.

6. The antimony-free flame-retardant ABS/CPE alloy material according to claim 1, wherein the antimony-free synergistic master batch does not contain antimony, and is a master batch prepared by processing silicon oxide/antimony synergist under a low-temperature condition by loading ethylene copolymer.

7. The antimony-free flame-retardant ABS/CPE alloy material as claimed in claim 1, wherein the kaolin is water-washed kaolin, and the crystal chemical formula of the kaolin is 2SiO₂·Al₂O₃·2H₂O, theoretical chemical composition of which is 46.54% SiO₂39.5% of Al₂O₃13.96% of H₂O。

8. The antimony-free flame-retardant ABS/CPE alloy material as claimed in claim 1, wherein the antioxidant is 1010 (pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), a poly hindered phenol type antioxidant, and a complementary antioxidant 168 (tris [2, 4-di-tert-butylphenyl ] phosphite), and is a phosphite antioxidant with excellent performance.

9. The antimony-free flame-retardant ABS/CPE alloy material as claimed in claim 1, wherein the hydrotalcite is a layered double hydroxide belonging to anionic layered compounds, has a certain alkalinity, and can neutralize hydrogen halide generated during processing of the modified flame-retardant resin.

10. The antimony-free flame retardant ABS/CPE alloy material according to claim 1, characterized in that the lubricant is Ethylene Bis Stearamide (EBS), calcium stearate or stearate salt of zinc stearate.

11. The antimony-free flame-retardant ABS/CPE alloy material as claimed in claim 1, wherein the anti-dripping agent is specially modified Polytetrafluoroethylene (PTFE) powder, and the solid content of the PTFE is greater than or equal to 99%.

12. A method for preparing the antimony-free flame retardant ABS/CPE alloy material according to any one of claims 1 to 11, characterized in that it comprises the following steps:

weighing raw materials of ABS, CPE, brominated flame retardant, char-forming flame-retardant synergist, silicon-boron flame-retardant synergist, antimony synergistic master batch, kaolin, hydrotalcite, antioxidant, lubricant, anti-dripping agent and the like according to the weight part ratio, putting the weighed raw materials into a mixer, setting the rotating speed of the mixer to be 200-300r/min, stirring for 2-5min, discharging after uniformly mixing, extruding and granulating by a double-screw extruder, wherein the rotating speed of a screw of the double-screw extruder is 500-600r/min, and the processing temperature is 180-200 ℃.

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to an antimony-free flame-retardant ABS/CPE alloy material and a preparation method thereof.

Background

The flame-retardant ABS has comprehensive good performances, including UL 94 5VA, 5VB and V0 grades, higher tensile, bending, impact resistance, HDT, CTI, glow wire and other performances, and can be applied to wide living fields, including the fields of automobile industry, office machines, household appliances and the like, although a small part of flame-retardant PS is replaced due to cost pressure in recent years, the flame-retardant PS has a very obvious gap with the flame-retardant ABS in the aspects of flame-retardant grade, mechanical strength and other performances, such as in the aspect of a strong electric control box, and the flame-retardant ABS is used as a raw material for production. Although in the market, halogen-free flame retardant ABS can better meet the environmental protection requirement of the present electronic products, due to the structural property (acrylonitrile-butadiene-styrene ternary copolymer) of ABS resin itself and the use limitation of halogen-free flame retardant (often need to fill in a large amount, make the original mechanical property of the resin matrix reduce too much), the flame retardant grade of the present halogen-free flame retardant ABS resin can not reach the level of the halogen-containing flame retardant ABS resin. At present, halogen-free flame-retardant products with excellent mechanical properties and flame-retardant properties comprise halogen-free PC/ABS, halogen-free PPE/PS and other alloys, but the high production cost of the resins limits the popularization and application of the resins. On the basis of halogen flame-retardant ABS, the invention introduces a new organic polymer resin phase to form an alloy to improve the performance of a matrix material, optimizes a flame-retardant system, and ensures that the modified flame-retardant material can reach the V0 flame-retardant grade with the thickness of 2.0mm, the ignition temperature of a glow wire reaches 750 ℃, the impact strength is more than or equal to 200J/m (IZOD), and the modified flame-retardant material has lower molding shrinkage and higher dimensional stability.

The flame retardant capability of flame retardant ABS is improved by introducing CPE and minerals into a flame retardant system, for example, Chinese application patent CN107964209A discloses that 30-45 parts of ABS powder, 60-75 parts of SAN granules, 0.5-2 parts of ethylene bis stearamide, 0.5-1.5 parts of composite antioxidant, 24-40 parts of composite flame retardant and 1-2 parts of toughening agent are added; wherein the composite flame retardant is a mixture of antimony trioxide (Sb 2O 3), Chlorinated Polyethylene (CPE), tetrabromobisphenol A, decabromodiphenylethane and bromotriazine, and the weight ratio is 2-3:2-3:2-3: 1-2: 1-2 and a production process thereof. Patent CN104530634A discloses an environment-friendly high-proportion regenerated ABS flame-retardant modified composition, and a preparation method and an application thereof, wherein the formula of the regenerated ABS flame-retardant modified composition comprises 70 parts of r-ABS, 30 parts of high-rigidity ABS resin, and tris (tri-bromophenyl) cyanurate: 10-25 parts; antimony-based flame retardant synergist: 0-1 part; phosphorus flame retardant synergist: 1-5 parts; a toughening agent: 5-15 parts; a compatilizer: 1-3 parts; inorganic powder: 1-5 parts of regenerated ABS flame-retardant modified composition and application thereof. Although the patent technology reaches the flame retardant rating of V0, the examples all add antimony flame retardant, and it is difficult to reach the flame retardant rating of V0 without adding antimony flame retardant. Patent 200910064277.X discloses a flame-retardant ABS resin, wherein 45-65% of ABS, 10-25% of flame retardant, 15-30% of intrinsic flame-retardant polymer, 2-10% of PLS nano composite material, 3-10% of chlorinated polyethylene CPE, about 30-50% of total amount of flame retardant, and low flame-retardant efficiency.

In the flame-retardant ABS modification scheme in the prior art, a large amount of flame retardants are usually added to the halogen-free flame-retardant system, and the flame retardants include phosphate organic flame retardants or inorganic flame retardants such as magnesium hydroxide, aluminum hydroxide and zinc borate, and the performance of the resin itself is usually greatly damaged by the introduction of the flame retardants, including tensile bending strength or impact resistance. And under the condition of introducing a large amount of the flame retardant, the flame retardant grade of the modified ABS is not high, and the flame retardant requirement of many products, such as the 5VA grade of UL-94, can not be met. Although the traditional flame-retardant ABS can have a stable flame-retardant effect, the mass proportion of the brominated flame retardant is about 16 percent and the mass proportion of the antimony trioxide is about 4.5 percent depending on the large amount of the brominated flame retardant, the cost is increased too high, and the antimony oxide (Sb) is added₂O₃) The excessive dependence greatly limits the production and application of the flame-retardant ABS material.

Disclosure of Invention

The invention aims to firstly ensure that the modified flame-retardant ABS resin has high-grade flame-retardant performance, and meets the flame-retardant requirements of UL 94-1.5 mm V0 and 5VB, and 2.0mm 5 VA. And the charring property and the heat absorption and transfer in the combustion process are improved by optimizing a flame retardant system, and the high-efficiency flame retardance is realized by not adding an antimony flame retardant.

In order to realize the purpose of the invention, the invention provides an efficient flame-retardant ABS alloy material, which comprises the following components in percentage by weight:

60-80% of ABS resin; 6-20% of CPE; 10-20% of brominated flame retardant; 3-6% of carbon-forming flame-retardant synergist, 2-4% of silicon-boron flame-retardant synergist, 1-2% of antimony synergistic master batch and 2-4% of kaolin; 1-2% of hydrotalcite; 0.2 to 0.5 percent of antioxidant; 0.5 to 1.0 percent of lubricant; 0.2 to 0.3 percent of anti-dripping agent.

The ABS resin is a terpolymer synthesized by acrylonitrile, butadiene and styrene, has excellent low-temperature impact resistance, high surface hardness and good chemical resistance and electrical property, comprises trademarks of AE8000 AE8200 AG10NP AG10AP12A 115A 1, LG HF380 HF390 HI100H HI121H, Jilin petrochemical 0215H and the like, and can be preferably one or more of the combinations.

The CPE is chlorinated polyethylene, is a saturated high polymer material, is white powder in appearance, is nontoxic and tasteless, has excellent weather resistance, ozone resistance, chemical medicine resistance and aging resistance, and has good oil resistance, flame retardance and coloring performance. Good toughness (flexibility at minus 30 ℃), good compatibility with other high polymer materials and higher decomposition temperature. Including 135a 3135713052362135, one or more combinations thereof may be preferred.

The introduction of the brominated flame retardants comprises decabromodiphenylethane, hexabromocyclododecane, tetrabromobisphenol A, bromotriazine and the like, so that the ABS/CPE alloy has a certain flame retardant function, but the flame retardant function is far beyond the preset design value of the invention, and other flame retardants are required to be introduced to play a synergistic flame retardant role to replace the position of an antimony flame retardant.

The carbon-forming flame-retardant synergist is an efficient flame retardant replacing antimony trioxide, is different from the zinc borate or hydrotalcite type synergist on the market, and can be used for preparing a flame retardant with the following weight percentage of 1: the flame-retardant ABS resin 1 can replace antimony trioxide in a traditional halogen flame-retardant ABS resin system, accelerate carbonization in the combustion process and absorb heat energy, thereby achieving the effects of flame retardance and smoke suppression.

The silicon-boron flame-retardant synergist is a composite product adopting silicon, tin, boron, fluorine and the like, and the synergistic flame retardant is used in a bromine and antimony compound flame-retardant system, so that the use amount of a bromine flame retardant and antimony oxide can be reduced simultaneously.

The antimony synergistic master batch does not contain antimony elements, is a master batch prepared by processing silicon oxide/antimony synergistic agent loaded by ethylene copolymer under a low-temperature condition, and not only can play a role in inflaming retarding, increase of glow wire temperature and the like, but also can reduce the attenuation of an inflaming retarding system to the impact capacity of the inflaming retarding ABS alloy.

The kaolin is water-washed kaolin, and has the characteristics of high purity, high whiteness and high mesh number, and the crystal chemical formula of the kaolin is 2SiO₂·Al₂O₃·2H₂O, theoretical chemical composition of which is 46.54% SiO₂39.5% of Al₂O₃13.96% of H₂The introduction of O, silicon oxide and aluminum oxide can improve the heat resistance and flame retardance of the system.

The antioxidant is 1010 (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester), a multi-element hindered phenol antioxidant, and an auxiliary antioxidant 168 (tri [2, 4-di-tert-butylphenyl ] phosphite), is a phosphite antioxidant with excellent performance, has strong extraction resistance and stable hydrolysis effect, can obviously improve the light stability of a product, and can effectively prevent the thermal degradation of the ABS alloy in the extrusion injection molding process.

The hydrotalcite is a layered double hydroxide, belongs to an anionic layered compound, is used as a novel inorganic functional material with a layered structure, and has a structure similar to brucite Mg (OH)₂The modified flame-retardant resin has certain alkalinity, and can neutralize hydrogen halide generated in the processing process of the modified flame-retardant resin and keep the stability of the system. And when burning, along with the rising of burning thing temperature, hydrotalcite can lose interlaminar moisture and combine moisture, can absorb the heat, and carbonate can turn into carbon dioxide under the higher temperature moreover, reduces the oxygen concentration of burning system, plays the effect of separation oxygen. It is through this large and rapid reduction of heat absorptionThe oxygen concentration mode plays a role in flame retardance in the modified flame-retardant ABS alloy resin.

The lubricant is vinyl bis stearamide (EBS), calcium stearate or stearate of zinc stearate, and through the internal lubrication and external lubrication, various components can be well mixed together, so that a good plasticizing effect is achieved, frictional heat between the lubricant and processing machinery such as a screw is reduced, and the resin has a good demolding effect in the processing and forming processes.

The anti-dripping agent is specially modified Polytetrafluoroethylene (PTFE) powder, the solid content of the PTFE is more than or equal to 99%, and the anti-dripping agent is added into a formula of thermoplastic plastics, plays a role in increasing the melt strength and the flexural modulus, has a flame-retardant anti-dripping effect, and helps the thermoplastic materials to reach higher flame-retardant standard. Compared with common polytetrafluoroethylene, the polytetrafluoroethylene has excellent dispersibility and easy operability, no agglomeration at normal temperature, no wrinkling of injection molded products, no crystal points of black and white products and particularly obvious improvement on the surface gloss of the products. Due to the good compatibility, impact strength is less affected in high impact formulations.

The flame retardant mechanism of the present invention mainly comprises: 1. the metal ion active component and the halogen flame retardant in the product act to increase the hydrogen halide reaction and release more effective flame inhibitor-metal halide; 2. the rapid reaction forms a carbonization layer, which has better insulation and heat insulation properties, thereby improving the flame retardance; 3. in the flame retardant process, the heat absorption capacity is large, which is beneficial to reducing the high temperature generated during combustion; 4. the silicon-boron flame-retardant synergist and the antimony synergistic master batch have combined action of weather flame retardance and condensed phase flame retardance under the assistance of other inorganic fillers, so that 1.5mm reaches V0 and 5VB grades, and 3.0mm reaches 5VA grade.

The components can be mixed in a high mixing pot according to the formula proportion, the mixing speed is 120-500rpm, the mixing time is 3-10min, then the mixture is added into an extruder (suitable for a double-screw co-rotating extruder), the temperature of the extruder is suitable for the processing temperature of the general flame-retardant ABS, the temperature of each area is 180-200 ℃, the temperature of a die head is 210 ℃, and the rotating speed of a screw is controlled at 400-600 revolutions per minute.

Detailed Description

The technical solutions of the present invention will be described in detail and fully with reference to the following specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

For a further understanding of the invention, reference will now be made in detail to the following examples and to the accompanying scale.