阅读说明：本技术 一种hips复合材料及其应用 (HIPS (high impact polystyrene) composite material and application thereof ) 是由 杜荣华 叶南飚 黄险波 付锦锋 王亮 李斌 黄池光 范聪成 丰楠楠 杨霄云 于 2019-09-16 设计创作，主要内容包括：本发明涉及一种HIPS复合材料及其应用,属于工程塑料技术领域。本发明的HIPS复合材料包括以下重量份的组分：苯乙烯-丁二烯接枝共聚树脂50-80份,阻燃剂15-30份,增韧剂0-10份,所述阻燃剂包括(a)溴系阻燃剂和(b)无机次磷酸盐或无机亚磷酸盐。本发明由于采用了特定的物质进行复配作为阻燃剂,且阻燃剂为特定用量,HIPS复合材料不仅能起到阻燃作用,且综合性能较好；此外,本发明的HIPS复合材料未采用含锑物质作为原料,以保证环保安全,避免了三氧化二锑的致癌风险。(The invention relates to a HIPS composite material and application thereof, belonging to the technical field of engineering plastics. The HIPS composite material comprises the following components in parts by weight: 50-80 parts of styrene-butadiene graft copolymer resin, 15-30 parts of flame retardant and 0-10 parts of toughening agent, wherein the flame retardant comprises (a) brominated flame retardant and (b) inorganic hypophosphite or inorganic phosphite. According to the invention, as the specific substances are adopted to be compounded as the flame retardant, and the flame retardant is in a specific dosage, the HIPS composite material not only can play a flame retardant role, but also has good comprehensive performance; in addition, the HIPS composite material does not adopt antimony-containing substances as raw materials, so that the environmental protection and safety are ensured, and the carcinogenic risk of antimony trioxide is avoided.)

1. The HIPS composite material is characterized by comprising the following components in parts by weight: 50-80 parts of styrene-butadiene graft copolymer resin, 15-30 parts of flame retardant and 0-10 parts of toughening agent, wherein the flame retardant comprises (a) brominated flame retardant and (b) inorganic hypophosphite or inorganic phosphite.

2. The HIPS composite of claim 1, wherein the flame retardant is 18 to 25 parts by weight.

3. The HIPS composite of claim 2, wherein the flame retardant has a weight ratio of (a) to (b) of (1-14): 2.

4. the HIPS composite of claim 3, wherein the flame retardant has a weight ratio of (a) to (b) of (1-5): 1.

5. the HIPS composite of claim 1, wherein the particle size of (b) in the flame retardant is 80 μm or less.

6. The HIPS composite of claim 5, wherein the particle size of (b) is 40 μm or less.

7. The HIPS composite of claim 1, further comprising a flame retardant synergist, wherein the flame retardant synergist is a polysiloxane.

8. The HIPS composite of claim 1, wherein the styrene-butadiene graft copolymer resin is 55 to 75 parts by weight.

9. The HIPS composite of claim 1, wherein at least one of the following (a) to (c):

(a) the brominated flame retardant is at least one of tetrabromobisphenol A, brominated triazine, brominated epoxy flame retardants, decabromodiphenylethane, decabromodiphenyl ether, brominated polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate and brominated polyacrylate;

(b) the inorganic hypophosphite is at least one of aluminum salt, calcium salt and barium salt, zinc salt and magnesium salt of the inorganic hypophosphite; the inorganic phosphite is at least one of aluminum salt, calcium salt and barium salt of inorganic phosphite, zinc salt and magnesium salt;

(c) the toughening agent is at least one of styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer and hydrogenated styrene-isoprene block copolymer.

10. A flame retardant article comprising the HIPS composite of any of claims 1-9.

11. The flame retardant article of claim 10, wherein the flame retardant article is an electronic component.

Technical Field

The invention relates to a HIPS composite material and application thereof, belonging to the technical field of engineering plastics.

Background

The styrene-butadiene graft copolymer resin, namely HIPS resin, has the performance between that of engineering plastics and general plastics, has excellent comprehensive mechanical property and processing and forming performance, and is widely applied to the fields of electronics, electrics, machinery, buildings and the like. However, the HIPS resin has many defects and shortcomings due to the limitation of the polymer structure and composition, such as poor wear resistance, low heat resistance, poor weather resistance, and only HB-level flame retardance. The HIPS resin is used as a matrix, and a certain amount and a certain proportion of brominated flame retardant and antimony-containing compound flame retardant synergist are added to prepare the flame-retardant HIPS with different vertical combustion grades.

At present, although the research on the halogen-free flame retardance of HIPS resin is great, the gap between the comprehensive performance of the halogen-free flame-retardant HIPS and the market application requirement is large, so that the flame-retardant system used by the flame-retardant HIPS on the market is mainly a bromine-antimony synergistic system. Bromine of the bromine-antimony synergistic system is mainly from common bromine flame retardants in the market, such as tetrabromobisphenol A, bromotriazine, decabromodiphenylethane, brominated polystyrene and the like; the antimony is mainly from flame retardant synergist of antimony-containing compound, such as antimony oxide, antimonate, etc. Among the antimony-containing flame retardant synergists, antimony trioxide is most commonly used.

However, in recent years, with the increasing concern of environmental protection and ecological safety, the laws and regulations in these areas are gradually perfected, and the ROHS directive of the european union is one of the environmental regulations with a relatively wide influence. Studies have found that antimony trioxide belongs to the class B carcinogen, and is considered to be listed in the ROHS restriction material list by the European Union in 2018, and is now in the stage of inquiry. Due to the risk of antimony trioxide being totally restricted and banned, the development of fire retardant systems that do not use antimony trioxide at all is imminent.

At present, no patent or literature reports on the brominated flame-retardant HIPS material which does not use antimony-containing compounds as a synergist.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a novel antimony-free flame-retardant HIPS composite material and application thereof.

In order to achieve the purpose, the invention adopts the technical scheme that: the HIPS composite material comprises the following components in parts by weight: 50-80 parts of styrene-butadiene graft copolymer resin (HIPS resin), 15-30 parts of flame retardant and 0-10 parts of toughening agent, wherein the flame retardant comprises (a) a brominated flame retardant and (b) inorganic hypophosphite or inorganic phosphite.

The styrene-butadiene graft copolymer resin (HIPS resin) is a conventional resin. The HIPS resin is a graft copolymer of butadiene rubber and styrene monomer, wherein the content weight ratio of butadiene is 2-20%, and the content weight ratio of styrene is 80-98%.

Research shows that when the flame retardant is less than 15 parts by weight, the flame retardant effect is poor, although the flame retardant effect is better when the flame retardant is more, once the flame retardant is more than 30 parts by weight, the comprehensive performance of the HIPS composite material can be affected, for example, the material is too brittle, the notch impact strength is low, the appearance is not good, and the like, so that the HIPS composite material is not easy to process and the application value is not high. The inorganic hypophosphite or inorganic phosphite is used as one of the components of the flame retardant, and the stability of the flame retardant is better than that of organic phosphine. More importantly, as the special substances are adopted to be compounded as the flame retardant, and the flame retardant is in a special dosage, the HIPS composite material not only can play a flame retardant role, but also has better comprehensive performance.

In addition, the HIPS composite material does not adopt antimony-containing substances as raw materials, so that the environmental protection and safety are ensured, and the carcinogenic risk of antimony trioxide is avoided.

The impact of the using amount of the flame retardant on the notched impact strength and the appearance of the HIPS composite material are comprehensively considered, and as a preferred embodiment of the HIPS composite material, the flame retardant is 18-25 parts by weight. More preferably, in the flame retardant, the weight ratio of (a) to (b) is (1-14): 2. more preferably, the weight ratio of (a) to (b) in the flame retardant is (1-5): 1.

in a preferred embodiment of the HIPS composite material of the present invention, the particle size of (b) in the flame retardant is 80 μm or less. More preferably, the particle diameter of (b) is 40 μm or less. The particle size of the inorganic hypophosphite or inorganic phosphite in the flame retardant can also influence the notch impact strength and the flame retardant property of the HIPS composite material, and when the particle size of the inorganic hypophosphite or inorganic phosphite is below 80 mu m, especially not higher than 40 mu m, the notch impact strength and the flame retardant stability of the HIPS composite material are improved. If the particle size of the inorganic hypophosphite or inorganic phosphite is too large, the HIPS composite material is too brittle to be used.

As a preferred embodiment of the HIPS composite material of the present invention, the HIPS composite material further comprises a flame retardant synergist, and the flame retardant synergist is polysiloxane. Polysiloxane is adopted as a flame retardant synergist, which is beneficial to improving the flame retardant property of the HIPS composite material.

As a preferred embodiment of the HIPS composite material, the flame-retardant synergist is less than 4 parts by weight.

As a preferred embodiment of the HIPS composite material of the present invention, the styrene-butadiene graft copolymer resin is 55 to 75 parts by weight.

As a preferred embodiment of the HIPS composite material of the present invention, at least one of the following (a) to (c):

(a) the brominated flame retardant is at least one of tetrabromobisphenol A, brominated triazine, brominated epoxy flame retardants, decabromodiphenylethane, decabromodiphenyl ether, brominated polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate and brominated polyacrylate;

(b) the inorganic hypophosphite is at least one of aluminum salt, calcium salt and barium salt, zinc salt and magnesium salt of the inorganic hypophosphite; the inorganic phosphite is at least one of aluminum salt, calcium salt and barium salt of inorganic phosphite, zinc salt and magnesium salt;

(c) the toughening agent is at least one of a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, a styrene-isoprene block copolymer and a hydrogenated styrene-isoprene block copolymer; preferably, in the styrene-butadiene block copolymer, the weight percentage of styrene is 30-95%, and the weight percentage of butadiene is 5-70%; in the hydrogenated styrene-butadiene block copolymer, the weight percentage of styrene is 30-60%, the weight percentage of butadiene is 40-70%, and the hydrogenation proportion is 30-100%; in the styrene-isoprene block copolymer, the weight percentage of styrene is 30-95%, and the weight percentage of isoprene is 5-70%; in the hydrogenated styrene-isoprene block copolymer, the weight percentage of styrene is 30-60%, the weight percentage of isoprene is 40-70%, and the hydrogenation ratio is 30-100%.

The preparation method of the HIPS composite material comprises the following steps: firstly, weighing each component in the HIPS composite material according to a proportion, and mixing in a mixer to obtain a mixed material; and then placing the mixed material in a double-screw extruder, extruding and granulating to obtain the HIPS composite material.

In addition, the invention also provides a flame-retardant product containing the HIPS composite material.

As a preferred embodiment of the flame retardant article of the present invention, the flame retardant article is an electronic component.

The HIPS composite material can be used in the electronic and electrical field with flame retardant requirements, the application field of replacing the original bromine and antimony flame retardant HIPS composite material, and other fields needing to use the flame retardant HIPS.

Compared with the prior art, the invention has the beneficial effects that: the invention provides a novel antimony-free flame-retardant HIPS composite material, which reduces potential environmental protection and personal safety risks of users and fills the market blank. The HIPS composite material can be used for electronic and electrical equipment parts with flame-retardant requirements, and can completely replace the application market of the traditional bromine-antimony system flame-retardant HIPS.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.