CN110964284A - Flame-retardant HIPS composite material - Google Patents
Flame-retardant HIPS composite material Download PDFInfo
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- CN110964284A CN110964284A CN201911280234.5A CN201911280234A CN110964284A CN 110964284 A CN110964284 A CN 110964284A CN 201911280234 A CN201911280234 A CN 201911280234A CN 110964284 A CN110964284 A CN 110964284A
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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
- 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
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Abstract
The invention discloses a flame-retardant HIPS composite material which comprises the following components in parts by weight: 60-96 parts of PS resin, 0-20 parts of toughening agent, 3-25 parts of flame retardant, 0.1-20 parts of flame retardant synergist and 0.01-1 part of anti-dripping agent; the flame retardant is a mixture of a flame retardant A and a flame retardant B; the flame retardant A is at least one of decabromodiphenylethane, brominated epoxy, brominated triazine, brominated imine, tetrabromobisphenol A and octabromoether; the flame retardant B is at least one of phosphate, melamine, polyphosphate, melamine polyphosphate and melamine cyanurate. The HIPS composite material is compounded by adopting the gas-phase flame retardant and the condensed-phase flame retardant, so that the flame retardant efficiency is high, the adding proportion of the two flame retardants is reduced, the cost is reduced, the product has market competitiveness, the smoke generation amount is small, the smell is small, and the physical and mechanical properties of the composite material are high.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant HIPS composite material.
Background
In the modern society, the requirement for the fire-proof safety of materials is higher and higher. Because the common flame retardants such as decabromodiphenyl ether generate a large amount of black smoke when being combusted, and even generate dioxin which is a strong carcinogenic substance, great harm is caused to human bodies, laws and regulations are generally issued in various countries, and the use of certain flame retardants is limited. In the field of household appliances and the like, there is a risk of short-circuit ignition due to contact with electricity, and thus flame retardancy is required for the material.
The gas-phase flame retardant represented by a brominated flame retardant used in a common environment-friendly flame-retardant PS system has high flame-retardant efficiency, but has the defects of large smoke generation amount and large smell, and smoke generated during fire can cause suffocation. Although the solidified phase flame retardant represented by phosphate generates less smoke, the solidified phase flame retardant has the defects of low flame retardant efficiency and easy precipitation, the physical and mechanical properties of the material are too low due to large addition amount, and V0 grade halogen-free flame retardant HIPS which is not commercially produced is not sold in the market.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a flame-retardant HIPS composite material.
In order to achieve the purpose, the invention adopts the technical scheme that: the flame-retardant HIPS composite material comprises the following components in parts by weight: 60-96 parts of PS resin, 0-20 parts of toughening agent, 3-25 parts of flame retardant, 0.1-20 parts of flame retardant synergist and 0.01-1 part of anti-dripping agent;
the flame retardant is a mixture of a flame retardant A and a flame retardant B; the flame retardant A is at least one of decabromodiphenylethane, brominated epoxy, brominated triazine, brominated imine, tetrabromobisphenol A and octabromoether; the flame retardant B is at least one of phosphate, melamine, polyphosphate, melamine polyphosphate and melamine cyanurate;
the PS resin is at least one of HIPS, GPPS and EPS.
At present, the commercially available environment-friendly flame-retardant V-0-grade HIPS uses a brominated flame retardant which is a gas-phase flame retardant, the flame retardant mechanism is that the flame retardant is decomposed in preference to resin when plastic burns to generate a large amount of inert gas, and the large amount of inert gas is enriched on the surface of the resin, so that oxygen is isolated, and the purpose of inhibiting the resin burning is achieved. In recent years, only V-2 grade halogen-free flame-retardant HIPS is commercialized at present, condensed phase flame retardants represented by phosphate ester are mainly used, and the flame retardant mechanism is that the flame retardant agent rapidly expands to form a porous carbon layer on the surface during combustion, so that oxygen is isolated, and resin combustion is inhibited.
The invention adopts the compounding of the gas-phase flame retardant and the condensed-phase flame retardant, and the flame retardant mechanism is as follows: after the novel flame retardant is added, an even carbon foam layer can be formed on the surface of HIPS (high impact polystyrene) during combustion, the carbon layer can play the roles of heat insulation, oxygen isolation, smoke suppression and molten drop prevention in a condensed phase, and inert gas generated by the brominated flame retardant is adsorbed in the middle of the porous carbon layer, so that the flame retardant effect is better. The HIPS composite material is a low-halogen flame-retardant HIPS composite material, solves the problems of low flame-retardant efficiency, large addition amount and great influence on the physical and mechanical properties of products of non-brominated flame retardants for a long time, reduces the use of brominated flame retardants, has low smoke generation amount and small smell, and realizes the efficient utilization of the flame retardants. The flame retardant efficiency is higher when the gas-phase brominated flame retardant and the condensed-phase flame retardant are compounded by adopting the flame retardants.
Preferably, the weight ratio of the flame retardant A to the flame retardant B is: flame retardant A: and the flame retardant B is 1-2: 1-2. The inventors found that when the two flame retardants are used in the above compounding ratio, the flame retardant efficiency is higher.
Preferably, the flame retardant A is decabromodiphenylethane and brominated epoxy; the flame retardant B is phosphate. The inventor finds that the flame retardant A is decabromodiphenylethane and brominated epoxy, and the flame retardant B is a phosphate compound, so that the flame retardant efficiency is superior to that of other compound combinations, and the fluidity is good.
Preferably, the weight percentage of the flame retardant in the flame-retardant HIPS composite material is 12-18%. When the flame retardant is added, the flame retardant can meet the flame retardant effect of V-0 level, and better mechanical properties can be ensured.
Preferably, the anti-dripping agent is polytetrafluoroethylene coated with acrylate. The addition of the anti-dripping agent can reduce the dosage of the flame retardant, so that the flame retardant can realize higher flame retardant grade under the condition of less dosage. Preferably, the anti-dripping agent is 0.05-0.15 part by weight. The anti-dripping agent can fully exert the effect on the premise of lower cost by adopting the dosage.
Preferably, the toughening agent is SBS.
Preferably, the flame retardant synergist is antimony trioxide and/or talcum powder.
Preferably, the flame-retardant HIPS composite material further comprises 0.1-2 parts by weight of an auxiliary agent, wherein the auxiliary agent comprises at least one of an antioxidant and a lubricant.
Preferably, the antioxidant is antioxidant 1010 and/or antioxidant 168.
Preferably, the lubricant is at least one of a stearate lubricant, a fatty acid lubricant and a stearate lubricant; the stearate lubricant is at least one of calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one of fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one of pentaerythritol stearate.
Preferably, the flame-retardant HIPS composite material consists of the following components in parts by weight: 60-96 parts of PS resin, 0-20 parts of toughening agent, 3-25 parts of flame retardant, 0.1-20 parts of flame retardant synergist, 0.01-1 part of anti-dripping agent and 0.1-2 parts of auxiliary agent.
The invention has the beneficial effects that: the invention provides a flame-retardant HIPS composite material, which is high in flame-retardant efficiency by compounding a gas-phase flame retardant and a condensed-phase flame retardant, reduces the addition ratio of the two flame retardants, reduces the cost, has market competitiveness, generates less smoke and has little smell, and meanwhile, the composite material has high physical and mechanical properties.
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.
Example 1
The raw materials in the examples and comparative examples were purchased from the market and the sources of the raw materials were as follows:
HIPS resin: selecting HIE-1 from Monoshan petrochemical company and HIPSMA5210 from Chevrolet philips; GPPS resin: selecting GPPS-500NT of a medium-oil-solitary petrochemical company and GPPS 123P of a Shanghai Seisaku petrochemical industry Limited liability company;
talcum powder is prepared from Italy Eimeria (IMIFABI) Talcum powder HTPUltra5L, wherein the length-diameter ratio of more than 90 wt% of particles in the Talcum powder of HTPUltra5L is not less than 5: 1;
SBS: SBS YH-792E of China petrochemical Basil petrochemical company is selected;
antioxidant: selecting a mixture prepared by compounding an antioxidant 1010 and an antioxidant 168 produced by Shanghai Ciba refining company according to the weight ratio of 1: 2;
the anti-dripping agent is acrylic ester coated polytetrafluoroethylene which is purchased from Pacific Interchem company and has a commercial model number of POLY TS 30A;
decabromodiphenylethane is SAYTEX 8010 from Abauba, USA;
the bromide imine is BT-93W of Shanghai Kangcheng chemical industry Co., Ltd;
brominated epoxy is F-3014 from Bromine Compounds Ltd.;
the brominated triazine is BTAC-245 of Wo Jin Copolymer Co.Ltd;
the phosphate is BDP-H of Yake science and technology Limited of Jiangsu;
the melamine polyphosphate is FR-NP of chemical industry Co., Ltd;
the melamine is MCA of Sichuan fine chemical engineering;
antimony trioxide is S-12N from the antimony flash industry.
The other auxiliary agent is lubricant, and zinc stearate BS-2818 of Zhongshan Huaming Tai chemical corporation is selected.
In the examples and comparative examples, the preparation method of the flame retardant HIPS composite material comprises the following steps: weighing PS resin, a flame retardant synergist, a toughening agent, an anti-dripping agent and an auxiliary agent according to a ratio, adding the materials into a high-speed mixer, uniformly mixing, and adding into a double-screw extruder. Wherein the length-diameter ratio of the double-screw extruder is 40: 1; the barrel temperature is set as follows: the temperature of a first area is 80 ℃, the temperature of a second area is 160 ℃, the temperature of a third area is 200 ℃, the temperature of a fourth area is 200 ℃, the temperature of a fifth area is 200 ℃, the temperature of a sixth area is 200 ℃, the temperature of a seventh area is 200 ℃, the temperature of an eighth area is 200 ℃, the temperature of a ninth area is 200 ℃, the temperature of a tenth area is 200 ℃ and the temperature of a machine head is 220 ℃; and (3) extruding and granulating at the screw rotating speed of 300 revolutions per minute to obtain the HIPS composite material.
The formulations of the flame retardant HIPS composite materials described in examples 1-25 and comparative examples 1-3 are shown in tables 1-3, respectively.
The relevant performances of the flame-retardant HIPS composite materials in the examples 1-25 and the comparative examples 1-3 are tested, and the test method comprises the following steps:
tensile strength was tested according to ISO 527;
elongation at break was tested according to ISO 527;
flexural modulus was tested according to ISO 178;
the bending strength is tested according to ISO 178;
cantilever beam impact strength (notch) was tested according to ISO 180;
the vertical burning rating is tested according to UL 94;
the test results are shown in tables 1-3.
Table 1 formulas and performance test results of the flame retardant HIPS composite materials described in examples 1 to 7 and comparative examples 1 to 3
Table 2 formula and performance test results of flame-retardant HIPS composite materials described in examples 8-13
Table 3 formulation and Performance test results for flame retardant HIPS composites described in examples 14-23
The impact strength of the added flame retardant on the cantilever beam is greatly influenced, generally speaking, when the impact strength of the cantilever beam is lower than 7, the falling test qualification rate of the HIPS material is low, and when the impact strength of the cantilever beam is higher than 8, the HIPS can meet the requirements of most users. As can be seen from tables 1 and 2, under the condition of a certain amount of the flame retardant, flame retardant effects of different types and proportions of flame retardants on HIPS materials are different. As can be seen from the comparison of examples 1 to 7 in Table 1, the ratio of the flame retardant A to the flame retardant B directly affects the flame retardant effect, and when the weight ratio of the flame retardant A to the flame retardant B is: flame retardant A: when the flame retardant B is in the range of 1 to 2:1 to 2 (examples 3 to 5), V-0 class can be achieved, impact properties are good, and combustion generates less smoke, and it can be seen from comparative example 2 and examples 1 to 2 that when only the flame retardant A is added or the weight ratio of the flame retardant A to the flame retardant B is more than 2:1, V-0 flame retardant class can be satisfied, but combustion generates more smoke. When only phosphate was added, the V-0 rating could not be achieved, and as can be seen from the comparison of comparative example 3 with example 4, comparative example 3 lacks the anti-dripping agent, and the flame retarding effect thereof is reduced.
As can be seen from comparison of the examples 8-13 in the table 2, when the flame retardant is decabromodiphenylethane and brominated epoxy matched with phosphate ester, the flame retardant effect of V-0 level can be realized by adding 12%, when other flame retardants A and B are used for compounding, the flame retardant effect of V-0 level cannot be realized by adding 12% of flame retardant, and the flame retardant effect can be realized by adding more flame retardants, which is lower than the flame retardant efficiency when decabromodiphenylethane and brominated epoxy are matched with phosphate ester.
In Table 3, the proportion of decabromodiphenyl ethane, brominated epoxy and phosphate as the flame retardant was substantially the same in examples 14 to 18 as compared with example 3, and the proportion of decabromodiphenyl ethane, brominated epoxy and phosphate as the flame retardant was substantially the same in examples 19 to 23 as compared with example 5, the total addition amount of the flame retardant was changed, when the total addition amount of the flame retardant was less than 12%, the flame retardancy grade did not reach the V-0 grade (examples 14 and 19), when the total addition amount of the flame retardant was more than 12%, the V-0 flame retardancy grade could be achieved, however, an increase in the amount of flame retardant added leads to a decrease in mechanical properties, mainly impact strength, when the amount of the flame retardant added is greater than 18%, the flame retardant increases, the impact strength decreases rapidly (examples 17, 18, 22, and 23), and it is difficult to satisfy the user's demand for high mechanical properties.
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 (10)
1. The flame-retardant HIPS composite material is characterized by comprising the following components in parts by weight: 60-96 parts of PS resin, 0-20 parts of toughening agent, 3-25 parts of flame retardant, 0.1-20 parts of flame retardant synergist and 0.01-1 part of anti-dripping agent;
the flame retardant is a mixture of a flame retardant A and a flame retardant B; the flame retardant A is at least one of decabromodiphenylethane, brominated epoxy, brominated triazine, brominated imine, tetrabromobisphenol A and octabromoether; the flame retardant B is at least one of phosphate, melamine, polyphosphate, melamine polyphosphate and melamine cyanurate;
the PS resin is at least one of HIPS, GPPS and EPS.
2. The flame retardant HIPS composite of claim 1, wherein the weight ratio of flame retardant a to flame retardant B is: flame retardant A: and the flame retardant B is 1-2: 1-2.
3. The flame retardant HIPS composite of claim 2, wherein the flame retardant a is decabromodiphenylethane and brominated epoxy; the flame retardant B is phosphate.
4. The flame retardant HIPS composite material of claim 2, wherein the flame retardant is present in the flame retardant HIPS composite material in an amount of 12 to 18% by weight.
5. The flame retardant HIPS composite of claim 1, wherein the anti-drip agent is an acrylate coated polytetrafluoroethylene.
6. The flame retardant HIPS composite of claim 1, wherein the toughening agent is SBS.
7. The flame retardant HIPS composite of claim 1, wherein the flame retardant synergist is antimony trioxide and/or talc.
8. The flame retardant HIPS composite of claim 1, further comprising 0.1 to 2 parts by weight of an auxiliary agent, wherein the auxiliary agent comprises at least one of an antioxidant and a lubricant heat stabilizer.
9. The flame retardant HIPS composite of claim 8, wherein the following (a) and/or (b):
(a) the antioxidant is an antioxidant 1010 and/or an antioxidant 168;
(b) the lubricant is at least one of stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one of calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one of fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one of pentaerythritol stearate.
10. The flame retardant HIPS composite of claim 1, which is comprised of the following components in parts by weight: 60-96 parts of PS resin, 0-20 parts of toughening agent, 3-25 parts of flame retardant, 0.1-20 parts of flame retardant synergist, 0.01-1 part of anti-dripping agent and 0.1-2 parts of auxiliary agent.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112662110A (en) * | 2020-12-21 | 2021-04-16 | 青岛润兴塑料新材料有限公司 | High-toughness flame-retardant PS micro-foaming material |
| CN112898713A (en) * | 2021-02-05 | 2021-06-04 | 深圳市富恒新材料股份有限公司 | Preparation method of low-cost flame-retardant HIPS material |
| CN114621534A (en) * | 2022-03-31 | 2022-06-14 | 国高材高分子材料产业创新中心有限公司 | PS-based standard sample for detecting flame retardant property and preparation method thereof |
| CN115181344A (en) * | 2022-07-28 | 2022-10-14 | 金发科技股份有限公司 | High-heat-resistance flame-retardant HIPS material and preparation method and application thereof |
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| CN115181344B (en) * | 2022-07-28 | 2023-08-22 | 金发科技股份有限公司 | High heat-resistant flame-retardant HIPS material and preparation method and application thereof |
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Application publication date: 20200407 |
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