CN110643132A - HIPS (high impact polystyrene) composite material and application thereof - Google Patents
HIPS (high impact polystyrene) composite material and application thereof Download PDFInfo
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- CN110643132A CN110643132A CN201910872666.9A CN201910872666A CN110643132A CN 110643132 A CN110643132 A CN 110643132A CN 201910872666 A CN201910872666 A CN 201910872666A CN 110643132 A CN110643132 A CN 110643132A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
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.
Description
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.
Examples 1 to 6
The components of the HIPS composite material of the embodiments 1-6 of the invention are shown in the following table 1.
The preparation method of the HIPS composite material in the embodiments 1-6 of the invention comprises the following steps: weighing the components in the HIPS composite material according to a proportion, putting the components into a mixer to mix for 5min at a rotating speed of 1000 rpm, taking out, putting the mixed materials into a feed hopper of a double-screw extruder, carrying out melt blending through a co-rotating double-screw extruder according to a set process (the temperature set range of each section of the extruder is 180 DEG and the screw rotating speed set range is 200 DEG) and then carrying out water cooling, drawing strips and pelletizing to obtain the HIPS composite material.
The performance test method comprises the following steps:
(1) and (3) testing the flame retardant grade: v-0, test standard UL94, bars 125mm 13mm 1.5 mm;
(2) notched impact strength test: performing injection molding to obtain a bar-shaped sample strip meeting the requirements of ISO 180 cantilever beam notch impact strength test, testing the notch impact strength at 25 ℃, and recording the strength data of the sample strip when the sample strip is broken;
(3) appearance defects: and (3) performing injection molding to obtain a square plate with the thickness of 100mm x 1.5mm, visually observing whether the surface of the square plate has obvious appearance defects such as white spots and the like, and recording the observation result.
The HIPS composite particles obtained by the method are dried and injection molded into test sample strips or square plates of corresponding types for testing the flame retardant property, and the test result of the flame retardant property is shown in Table 1.
TABLE 1
As can be seen from Table 1, the HIPS composite material of the present invention has both good flame retardant properties and good notched impact strength.
Effect example 1
The effect example investigates the influence of the flame retardant in the HIPS composite material on the notch impact strength and the flame retardant performance of the HIPS composite material, and simultaneously investigates the influence of the flame retardant synergist on the flame retardant performance of the HIPS composite material. The specific method for investigation is as follows: in the effect example, the HIPS composite materials of the test groups 1 to 12 were prepared according to the preparation methods of the HIPS composite materials of the embodiments 1 to 6. The HIPS composite material for the test groups 1-112 comprises the following components: 50-80 parts of styrene-butadiene graft copolymer resin, 0-10 parts of flame retardant, toughening agent and less than 4 parts of flame retardant synergist; wherein the parts all represent parts by weight, the flame retardant consists of (a) a brominated flame retardant and (b) an inorganic hypophosphite or an inorganic phosphite, the parts by weight of the flame retardant and the proportion of the (a) and the (b) are shown in the following table 2, and the particle size of the inorganic hypophosphite or the inorganic phosphite is less than 80 μm; 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; 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; 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; the flame-retardant synergist is polysiloxane.
The HIPS composite materials in test groups 1-12 are the same except that the amount of the flame retardant/polysiloxane and the proportion of the flame retardant/polysiloxane are different. The flame retardant property and the notched impact strength of the HIPS composite material prepared by the effect example are tested according to the HIPS composite material performance testing method of the examples 1-6, and the results are shown in Table 2.
TABLE 2
As can be seen by comparing the test groups 1 to 9, the HIPS composite material has the advantages that the more flame retardants, the better the flame retardant property; however, when the amount of the flame retardant is too much, the notched impact strength of the HIPS composite is lowered. Considering the flame retardant performance and the notch impact strength comprehensively, the flame retardant is preferably 18-25 parts by weight, and particularly, when the weight ratio of (a) the brominated flame retardant to (b) the inorganic hypophosphite or inorganic phosphite is (1-5): 1, the combination property is better. In addition, comparing test group 10 with test group 8, test group 11 with test group 6, and test group 12 with test group 1, respectively, it was found that the flame retardant property of the HIPS composite material of the present invention can be improved by using polysiloxane as the flame retardant synergist.
Effect example 2
The effect example investigates the influence of the particle size of the inorganic hypophosphite or inorganic phosphite in the HIPS composite material on the notch impact strength and the flame retardant property of the HIPS composite material. The specific method for investigation is as follows: in the effect example, the HIPS composite materials of the test groups 1 to 6 were prepared according to the preparation methods of the HIPS composite materials of the embodiments 1 to 6. The HIPS composite material of the test groups 1-6 comprises the following components: 50-80 parts of styrene-butadiene graft copolymer resin, 15-30 parts of flame retardant and 0-10 parts of toughening agent; wherein, the parts all represent parts by weight, the flame retardant consists of (a) a bromine flame retardant and (b) an inorganic hypophosphite or an inorganic phosphite, and the particle diameter of (b) in the flame retardant is shown in the following table 3; 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; 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; 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.
The HIPS composite materials in test groups 1-6 are the same except that the particle size of the flame retardant (b) is different. The flame retardant property and the notched impact strength of the HIPS composite material prepared by the effect example were tested according to the HIPS composite material performance test method of examples 1-6, and the results are shown in Table 3.
TABLE 3
As can be seen from Table 3, when the particle size of the inorganic hypophosphite or inorganic phosphite exceeds 80 μm, the notched impact strength and flame retardant properties of the HIPS composite are poor; when the particle size of the inorganic hypophosphite or inorganic phosphite is less than 40 mu m, the HIPS composite material has better notch impact strength and flame retardant stability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (11)
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.
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| CN201910872666.9A CN110643132A (en) | 2019-09-16 | 2019-09-16 | HIPS (high impact polystyrene) composite material and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268138A (en) * | 2005-07-22 | 2008-09-17 | 伊塔尔麦奇化学股份公司 | Flame retardant polymeric compositions |
| CN104334622A (en) * | 2012-05-24 | 2015-02-04 | Icl-Ip美国有限公司 | Antimony-free flame-retarded styrenic thermoplastic polymer composition, article containing same and method of making same |
| CN106147213A (en) * | 2015-04-02 | 2016-11-23 | 杜邦公司 | Fire-resistant polyamide composite |
| WO2018178985A1 (en) * | 2017-03-30 | 2018-10-04 | Bromine Compounds Ltd. | Flame-retarded styrene-containing formulations |
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2019
- 2019-09-16 CN CN201910872666.9A patent/CN110643132A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101268138A (en) * | 2005-07-22 | 2008-09-17 | 伊塔尔麦奇化学股份公司 | Flame retardant polymeric compositions |
| CN104334622A (en) * | 2012-05-24 | 2015-02-04 | Icl-Ip美国有限公司 | Antimony-free flame-retarded styrenic thermoplastic polymer composition, article containing same and method of making same |
| CN106147213A (en) * | 2015-04-02 | 2016-11-23 | 杜邦公司 | Fire-resistant polyamide composite |
| WO2018178985A1 (en) * | 2017-03-30 | 2018-10-04 | Bromine Compounds Ltd. | Flame-retarded styrene-containing formulations |
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