CN111154215A - Efficient halogen-free flame-retardant HIPS (high impact polystyrene) composite material and preparation method thereof - Google Patents
Efficient halogen-free flame-retardant HIPS (high impact polystyrene) composite material and preparation method thereof Download PDFInfo
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- CN111154215A CN111154215A CN202010099411.6A CN202010099411A CN111154215A CN 111154215 A CN111154215 A CN 111154215A CN 202010099411 A CN202010099411 A CN 202010099411A CN 111154215 A CN111154215 A CN 111154215A
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/22—Halogen free composition
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Abstract
The invention belongs to the technical field of composite materials, and discloses a high-efficiency halogen-free flame-retardant HIPS composite material and a preparation method thereof. The composition in the composite material consists of 20-30% of SBS, 5-10% of halogen-free toughening flame retardant, 1-5% of flame retardant synergist and 55-80% of HIPS. The toughening flame retardant has the effects of high-efficiency flame retardance, no halogen, no toxicity, molten drop prevention, smoke suppression and the like, and the composite material has better flame retardance through the synergistic effect of the toughening flame retardant and the flame retardant synergist; meanwhile, the flame retardant also has a toughening effect, can improve the toughness of the composite material together with SBS, and is simple in process, low in cost, high in product yield and suitable for large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a high-efficiency halogen-free flame-retardant HIPS composite material.
Background
In China, the main consumer field of High Impact Polystyrene (HIPS) is electronic and electric products, which account for about 50% of all plastic products. However, HIPS is easy to burn in case of fire during use and releases a large amount of smoke and harmful gases. With further strengthening and attention paid to the requirements of safety and environmental protection in China, the HIPS product must meet certain flame retardant requirements, has good flame retardant property and small smoke degree in big fire. However, the properties of the currently used flame retardant HIPS are not satisfactory.
Currently, HIPS is modified by adding a flame retardant to achieve flame retardant performance. However, most of the prior art adopts halogen flame retardants, which are cheap, but generate toxic gases and carcinogenic substances in the combustion process, thus being harmful to human health, and the halogen flame retardants are gradually stopped being used in the world. Therefore, halogen-free flame retardants are the hot spot of research and development at present. The invention patent CA 110315614A provides a melamine polyphosphate flame retardant, a preparation method and application thereof, and the product has the characteristics of excellent flame retardant effect, convenient construction, good heat resistance and the like. The invention patent CA 109971037A discloses a phosphorus-containing flame retardant, which can improve the compatibility of the nano flame retardant in polyester by mainly forming a molecular layer of ammonium phosphate on the surface of a halloysite nanotube, thereby improving the dispersibility and improving the flame retardant effect. The invention patent CA 110128836A discloses a phosphorus-silicon flame retardant which is mainly prepared by the reaction of phenyl phosphoryl dichloride and hydroxyl-terminated silicone oil, but the raw material of the phenyl phosphoryl dichloride is combustible and has certain toxicity although the raw material contains flame retardant element phosphorus. The invention patent CA 109054023A discloses a phosphorus-silicon flame retardant, which is prepared by adopting a grafting reaction of polyhydrosilsesquioxane and phosphate ester, silicon and phosphorus are used for realizing synergistic flame retardance, and the flame retardant effect of the flame retardant can be effectively improved. However, in the existing process of preparing the flame retardant, halogen element-containing raw materials are directly or indirectly used, and the raw materials can release a large amount of toxic, harmful and even carcinogenic halogen compounds such as hydrogen chloride or ammonium chloride and the like in the reaction process, so that the harm to human bodies or environment is caused, and the preparation process is very complicated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-efficiency halogen-free flame-retardant HIPS composite material.
The invention provides a high-efficiency halogen-free flame-retardant HIPS composite material which is characterized by comprising the following components in percentage by mass: 20-30% of SBS, 5-10% of halogen-free toughening flame retardant, 1-5% of flame retardant synergist and 55-80% of HIPS.
Preferably, the halogen-free toughening flame retardant is prepared by reacting sodium silicate and phosphoric acid for 1-4 hours at 40-60 ℃ in water bath to generate a silicic acid gel product with a molecular formula of H4SiO4。
Preferably, the modulus of the sodium silicate is 2.0-3.0, and the concentration of the phosphoric acid is more than or equal to 50%.
Preferably, the modulus of the sodium silicate is 2.6-3.0, and the concentration of the phosphoric acid is more than or equal to 85%.
Preferably, the SBS is prepared by a one-pot preparation process, the appearance is milky white, the viscosity is more than or equal to 4000 cp, and the molecular weight is 15000-20000 g/mol.
Preferably, the flame retardant synergist is zinc stannate.
The invention also provides a preparation method of the high-efficiency halogen-free flame-retardant HIPS composite material, which comprises the following steps:
(1) adding sodium silicate and phosphoric acid into a reaction kettle, and reacting for 1-4 hours in a water bath at 40-60 ℃ to obtain a halogen-free toughening flame retardant for later use;
(2) starting the double-screw extruder, setting the feeding speed and the screw rotating speed, starting the feeding machine to add the uniformly mixed halogen-free toughening flame retardant, flame retardant synergist, SBS and HIPS into the machine barrel, and performing melt blending and extrusion granulation to obtain the halogen-free high-efficiency flame retardant HIPS composite material.
The high-efficiency halogen-free flame-retardant HIPS composite material and the preparation method thereof provided by the invention have the following positive effects in the use process: (1) the adopted halogen-free toughening flame retardant is an environment-friendly phosphorus-silicon composite flame retardant, does not use halogen-containing raw materials, has higher thermal stability, and can play a role in synergy with the flame retardant synergist, so that the composite material has better flame retardance; (2) the halogen-free toughening flame retardant is prepared by reacting 2.6-3.0 modulus sodium silicate with phosphoric acid, and ductile crack bridges are formed in plastic deformation areas with cracks on a substrate by ductile particles of silicic acid to improve the toughness of the substrate. (3) The preparation method of the flame retardant has the advantages of simple process, low-temperature synthesis, environmental protection, safety, good repeatability and convenience for realizing industrialization; the HIPS high-efficiency flame-retardant composite material has mature preparation process and high production efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment of the invention provides a high-efficiency halogen-free flame-retardant HIPS composite material and a preparation method thereof, which comprises the steps of firstly adding 5kg of sodium silicate (modulus 2.0) and 10kg of phosphoric acid (60%) into a reaction kettle, reacting for 4 hours at 40 ℃ in a water bath condition to obtain a halogen-free toughening flame retardant, then adding 50kg of SBS, 5kg of flame-retardant synergist and 100kg of HIPS into a melt blending machine barrel, and preparing the high-efficiency flame-retardant composite material through a processing mode of extrusion granulation.
Example 2
The embodiment of the invention provides a high-efficiency halogen-free flame-retardant HIPS composite material and a preparation method thereof, which comprises the steps of firstly adding 10kg of sodium silicate (modulus 3.0) and 10kg of phosphoric acid (85%) into a reaction kettle, reacting for 3 hours at 50 ℃ in a water bath condition to obtain a halogen-free toughening flame retardant, then adding 70kg of SBS, 3kg of flame-retardant synergist and 160kg of HIPS into a melt blending machine barrel, and preparing the high-efficiency flame-retardant composite material through a processing mode of extrusion granulation.
Example 3
The embodiment of the invention provides a high-efficiency halogen-free flame-retardant HIPS composite material and a preparation method thereof, which comprises the steps of firstly adding 15kg of sodium silicate (modulus 2.8) and 15kg of phosphoric acid (80%) into a reaction kettle, reacting for 2 hours under the condition of water bath at 60 ℃ to obtain a halogen-free toughening flame retardant, then adding 80kg of SBS, 5kg of flame-retardant synergist and 200kg of HIPS into a melt blending machine barrel, and preparing the high-efficiency flame-retardant composite material through a processing mode of extrusion granulation.
Example 4
The embodiment of the invention provides a high-efficiency halogen-free flame-retardant HIPS composite material and a preparation method thereof, which comprises the steps of firstly adding 20kg of sodium silicate (modulus 2.5) and 10kg of phosphoric acid (75%) into a reaction kettle, reacting for 1 h under the condition of water bath at 60 ℃ to obtain a halogen-free toughening flame retardant, then adding 120kg of SBS, 20kg of flame-retardant synergist and 350kg of HIPS into a melt blending machine barrel, and preparing the high-efficiency flame-retardant composite material through a processing mode of extrusion granulation.
The performance tests of the examples 1-4 are carried out, wherein the comparative example 1 is HIPS added with a common flame retardant on the market, the comparative example 2 is HIPS without the flame retardant, and the test results are shown in the following table.
As can be seen from the above table: according to the SBS modified HIPS high-efficiency flame-retardant composite material, the flame retardant and the flame-retardant synergist are synergistic, so that the composite material has excellent flame retardance, the flame retardant grade reaches V-0, and the flame retardant grade is superior to that of a comparison sample; meanwhile, the flame retardant has a certain toughening effect by virtue of the mutual reaction of sodium silicate and phosphoric acid, so that the composite material has better toughness.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. The efficient halogen-free flame-retardant HIPS composite material is characterized by comprising the following components in parts by mass: 20-30% of SBS, 5-10% of halogen-free toughening flame retardant, 1-5% of flame retardant synergist and 55-80% of HIPS.
2. The efficient halogen-free flame retardant HIPS composite material as set forth in claim 1, wherein: the halogen-free toughening flame retardant is prepared by reacting sodium silicate and phosphoric acid for 1-4 hours at 40-60 ℃ in water bath to generate a silicic acid gel product with a molecular formula of H4SiO4。
3. The efficient halogen-free flame-retardant HIPS composite material as claimed in claim 2, wherein the modulus of the sodium silicate is 2.0-3.0, and the concentration of the phosphoric acid is more than or equal to 50%.
4. The efficient halogen-free flame-retardant HIPS composite material as claimed in claim 3, wherein the modulus of the sodium silicate is 2.6-3.0, and the concentration of the phosphoric acid is more than or equal to 85%.
5. The efficient halogen-free flame retardant HIPS composite material as set forth in claim 1, wherein: the SBS is prepared by a one-pot preparation process, is milk white in appearance, has the viscosity of more than or equal to 4000 cp, and has the molecular weight of 15000-20000 g/mol.
6. The efficient halogen-free flame retardant HIPS composite material as set forth in claim 1, wherein: the flame retardant synergist is zinc stannate.
7. The efficient halogen-free flame-retardant HIPS composite material according to claim 1, wherein the preparation method of the halogen-free flame-retardant HIPS composite material is as follows:
(1) adding sodium silicate and phosphoric acid into a reaction kettle, and reacting for 1-4 hours in a water bath at 40-60 ℃ to obtain a halogen-free toughening flame retardant for later use;
(2) starting the double-screw extruder, setting the feeding speed and the screw rotating speed, starting the feeding machine to add the uniformly mixed halogen-free toughening flame retardant, flame retardant synergist, SBS and HIPS into the machine barrel, and performing melt blending and extrusion granulation to obtain the halogen-free high-efficiency flame retardant HIPS composite material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010099411.6A CN111154215A (en) | 2020-02-18 | 2020-02-18 | Efficient halogen-free flame-retardant HIPS (high impact polystyrene) composite material and preparation method thereof |
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| CN202010099411.6A CN111154215A (en) | 2020-02-18 | 2020-02-18 | Efficient halogen-free flame-retardant HIPS (high impact polystyrene) composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521207A (en) * | 2003-01-27 | 2004-08-18 | 广州金发科技股份有限公司 | Halide-free flame-resistant high anti-impact polystyrene complex and method for production thereof |
| CN101787236A (en) * | 2010-01-30 | 2010-07-28 | 北京振利节能环保科技股份有限公司 | Fireproof interface agent for polystyrene foam heat insulation material and preparation method thereof |
-
2020
- 2020-02-18 CN CN202010099411.6A patent/CN111154215A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1521207A (en) * | 2003-01-27 | 2004-08-18 | 广州金发科技股份有限公司 | Halide-free flame-resistant high anti-impact polystyrene complex and method for production thereof |
| CN101787236A (en) * | 2010-01-30 | 2010-07-28 | 北京振利节能环保科技股份有限公司 | Fireproof interface agent for polystyrene foam heat insulation material and preparation method thereof |
Non-Patent Citations (4)
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| 刘文郁等: "《阿刀亥煤矿急倾斜特厚煤层综放开采技术与工程实践》", 31 August 2016, 中国矿业大学出版社, pages: 155 - 156 * |
| 吴世敏等: "《简明精细化工大辞典》", 30 June 1999, 辽宁科学技术出版社, pages: 643 - 644 * |
| 朱洪法等: "《无机化工产品手册》", 31 December 2008, 金盾出版社, pages: 10 * |
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