CN112852015A - Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof - Google Patents

Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof Download PDF

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CN112852015A
CN112852015A CN202110031101.5A CN202110031101A CN112852015A CN 112852015 A CN112852015 A CN 112852015A CN 202110031101 A CN202110031101 A CN 202110031101A CN 112852015 A CN112852015 A CN 112852015A
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flame retardant
brominated
composite
retardant
mass
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钱立军
王靖宇
杨海洲
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SHANDONG RUNKE CHEMICAL CO LTD
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SHANDONG RUNKE CHEMICAL CO LTD
Beijing Technology and Business University
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Priority to ES202230013A priority patent/ES2932703A1/en
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Abstract

本发明公开了一种高热稳定性的复合溴系阻燃剂及其阻燃聚苯乙烯材泡沫料，是在聚苯乙烯中添加特定复合阻燃体系获得高热稳定性的且不影响聚苯乙烯材料发泡的技术；具体是首先制备一种含有热稳定体系和氢溴酸吸收剂和抗氧剂的复合阻燃剂，可以实现在聚苯乙烯泡沫材料加工过程中阻燃剂的热稳定化；然后将该复合阻燃剂与聚苯乙烯熔融共混并加入发泡剂挤塑成发泡XPS材料，该阻燃体系获得的阻燃聚苯乙烯泡沫材料成型发泡工艺性能良好，在较低的阻燃剂添加量下使挤出发泡聚苯乙烯(XPS)实现良好的阻燃性能，并且保持了材料的物理机械性能和产品外观的颜色。The invention discloses a composite brominated flame retardant with high thermal stability and a flame retardant polystyrene foam material. The technology of material foaming; specifically, a composite flame retardant containing a thermal stabilization system, a hydrobromic acid absorbent and an antioxidant is first prepared, which can realize thermal stabilization of the flame retardant during the processing of polystyrene foam materials. Then the composite flame retardant is melted and blended with polystyrene and added with a foaming agent to be extruded into a foamed XPS material. The extruded expanded polystyrene (XPS) achieves good flame retardant performance with low flame retardant addition, and maintains the physical and mechanical properties of the material and the color of product appearance.

Description

Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof
Technical Field
The invention relates to a composite brominated flame retardant with high thermal stability and a preparation method of a flame-retardant polystyrene foam material thereof, belonging to the technical field of obtaining the flame-retardant polystyrene foam material by adding specific flame-retardant components into polystyrene.
Background
Polystyrene (PS) resin is one of five general plastics, and an extrusion molding type polystyrene insulation board (XPS) is a hard foamed board which is formed by adding a foaming agent into PS serving as a main raw material in a melting plasticizing process and then extruding; XPS has the advantages of economy, low water absorption, high mechanical strength, excellent heat insulation performance and the like, and is widely applied to commercial and civil external wall heat insulation materials; however, common polystyrene is combustible and inflammable, and at present, a large number of fires are caused by the fact that the outer wall heat-insulating material of the building adopts combustible polystyrene with high smoke content; therefore, flame retardant treatment of XPS to make it non-flammable when exposed to open flame or self-extinguishing when away from a fire source is important.
As the most important national building energy-saving and heat-insulating material at present, XPS mainly adopts Hexabromocyclododecane (HBCD) as a flame-retardant auxiliary agent at present, but the auxiliary agent is already listed in the forbidden list of the International convention of Stockholm due to persistent organic pollution; at present, the domestic building energy-saving field urgently needs the green environment-friendly alternative flame retardant to be applied to the expanded polystyrene heat-insulating material, which is very key for the nation to realize the aim of building an environment-friendly and resource-saving society; the current products capable of replacing HBCD only comprise two products, namely brominated styrene-butadiene-styrene block copolymer (brominated SBS) and methyl octabromoether; brominated SBS due to free small molecular fragments and methyl octabromoether due to active brominated aliphatic hydrocarbon can decompose and release hydrogen bromide in a processing temperature range, which is corrosive to production equipment and causes damage to the foaming performance and flame retardant performance of the XPS and discoloration of products in the production process of the XPS by blending, melting, extruding and foaming the polystyrene; therefore, a matched thermal stability system must be introduced in the process of producing the XPS material by taking brominated SBS and methyl octabromoether as flame retardants, so that the processing performance of XPS and the forming stability and the flame retardant performance of the foaming material are ensured.
At present, certain researches are carried out on the synthesis of brominated SBS and methyl octabromoether, such as patent applications CN111116782A, CN107474165B and CN109762121A of the brominated SBS and patent applications CN109796315A and CN109336746A of the methyl octabromoether, and the researches are dedicated to reducing the generation of free bromine in the synthesis process so as to improve the thermal stability of the flame retardant, but the chain breaking and decomposition of the flame retardant inevitably occur in the thermal processing process, so that the forming performance of the corresponding polystyrene foam material is influenced, the compatibility between the polystyrene foam material and a polymer matrix is reduced, the processing performance and the mechanical property of the flame retardant XPS material are obviously reduced, and the industrial requirements on the material performance are difficult to meet; the existing stearate heat stabilizer has a certain effect on improving the thermal stability of the brominated flame retardant, but cannot meet the requirement on the thermal stability of the two materials of the brominated SBS and the methyl octabromoether at present, so that a new thermal stability system which has a better thermal stability effect and does not influence the foaming performance of the polystyrene and a composite brominated flame retardant system with high thermal stability still need to be developed.
Disclosure of Invention
Aiming at the problems existing at present, the invention provides a high-thermal-stability composite brominated flame retardant containing a heat stabilizer, a hydrogen bromide absorbent and an antioxidant; the composite brominated flame retardant with high thermal stability is prepared by adding one or a mixture of brominated SBS and methyl octabromoether, adding a heat stabilizer, a hydrogen bromide absorbent and an antioxidant, melting, plasticizing and foaming the composite flame retardant, polystyrene, talcum powder, a foaming agent and the like, and extruding to obtain the flame-retardant polystyrene foam material.
The brominated flame retardant is one or a mixture of brominated SBS and methyl octabromoether, and the molecular formulas of the brominated SBS and the methyl octabromoether are respectively as follows:
Figure BDA0002892119340000031
the used raw materials are as follows: brominated SBS, methyl octabromo ether, stearate (selected from calcium stearate, zinc stearate, barium stearate), bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, brominated epoxy resin, tribromophenol glycidyl ether, divinylbenzene, triallyl triazine trione, talcum powder, polystyrene (selected from general purpose polystyrene, recycled polystyrene), foaming agent (selected from freon, ethanol, water, carbon dioxide), and antioxidant 1010 and 168.
Firstly, mixing one or two of brominated SBS and methyl octabromoether to form 100 parts by mass of flame retardant; and (2) mixing 0.5-20 parts by mass of heat stabilizer, 0.1-2 parts of antioxidant and 0.1-4 parts of hydrogen bromide absorbent with 100 parts by mass of flame retardant to obtain the composite brominated flame retardant with high heat stabilizer.
Wherein the heat stabilizer is formed by mixing one or more of calcium stearate, zinc stearate and barium stearate; the hydrogen bromide absorbent is formed by mixing one or more of bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, low molecular weight brominated epoxy resin, tribromophenol glycidyl ether, divinyl benzene and triallyl triazine Trione (TAIC), wherein the molecular weight of the low molecular weight brominated epoxy resin is 750-900, and the absorption capacity is stronger; the antioxidant is formed by mixing 1010 and 168.
And (2) adding one or a mixture of more of foaming agents of freon, ethanol, water and carbon dioxide into 0.5-20 parts by mass of the high-thermal-stability composite brominated flame retardant prepared in the first step, 0-5 parts by mass of talcum powder and 100 parts by mass of polystyrene in the process of melt blending to prepare the flame-retardant foamed polystyrene material.
Compared with the application of adopting a stearate heat stabilizer by simple assumption, the hydrogen bromide absorbent is creatively added into the composite system, so that the bromine flame retardant is more efficiently thermally stabilized; the composite brominated flame retardant and the flame-retardant polystyrene foam material thereof obtained by the method have high thermal stability in a thermal weight loss test, compared with a pure flame retardant system, the 1 wt% decomposition temperature of the composite brominated flame retardant is increased by 10 ℃ to 261 ℃, compared with the flame retardant discoloration temperature of 210 ℃, the composite brominated flame retardant does not discolor before 225 ℃, the prepared XPS board keeps a white state, and the foaming rate of the XPS board can reach 50 times; when the addition amount of the flame retardant is 0.5%, the Limit Oxygen Index (LOI) value of the obtained flame-retardant XPS material is up to 25.4%; when the addition amount is 3.5%, the LOI value is as high as 32.0%, and the apparent density of the obtained XPS foam board is 29.5kg/m3The thermal conductivity was 0.034W/m.k, and the compressive strength was 304 kPa.
Detailed Description
The invention is a technology that a specific composite flame-retardant system is added into polystyrene to obtain a high-thermal-stability material without influencing the foaming of the polystyrene material; firstly, preparing a composite brominated flame retardant containing a thermal stabilization system, a hydrobromic acid absorbent and an antioxidant, and realizing the thermal stabilization of the flame retardant in the processing process of the polystyrene foam material; and then the composite flame retardant is melted and blended with polystyrene, a foaming agent is added, and the mixture is extruded and molded to form the foaming XPS material, the flame-retardant polystyrene foam material obtained by the flame-retardant system has good molding and foaming process performance, the extruded and foamed polystyrene (XPS) realizes good flame-retardant performance under the condition of low addition of the flame retardant, and the physical and mechanical properties of the material and the color of the appearance of the product are maintained.
The following is illustrated with reference to specific examples:
example 1
150g of brominated SBS, 40g of methyl octabromoether, 2.5g of calcium stearate, 2.5g of zinc stearate, 5g of TAIC, 0.5g of antioxidant 1010 and 0.3g of antioxidant 168 are mixed into the composite brominated flame retardant, the composite flame retardant does not change color at the temperature of 235 ℃, the decomposition temperature of 1wt percent of the composite brominated flame retardant is 261 ℃, then 0.7kg of the composite brominated flame retardant, 0.05kg of talcum powder and 19.25kg of general polystyrene are continuously melted and blended in a double screw unit, and freon/CO is adopted2The/ethanol/water combined foaming agent is extruded and foamed. The apparent density of the obtained flame-retardant XPS material containing 3.5 percent of composite brominated flame retardant mass fraction is 29.5kg/m3The thermal conductivity was 0.034W/m.k, the compressive strength was 304kPa, the limiting oxygen index was 32.0%, and the XPS plate was white.
Example 2
285g of brominated SBS, 30g of calcium stearate, 15g of brominated epoxy resin, 0.5g of antioxidant 1010 and 0.3g of antioxidant 168 form a composite brominated flame retardant, the thermal decomposition temperature of the composite flame retardant is 225 ℃ and does not change color, the decomposition temperature of 1 wt% of the composite brominated flame retardant is 255 ℃, then 0.3kg of the composite brominated flame retardant, 0.1kg of talcum powder and 19.6kg of general polystyrene are continuously melted and blended in a double-screw unit, and CO is adopted2Performing extrusion molding foaming on the/ethanol/water combined foaming agent; the apparent density of the obtained flame-retardant XPS material containing 1.5 percent of composite brominated flame retardant mass fraction is 29.3kg/m3The thermal conductivity was 0.034W/m.k, the compressive strength was 305kPa, the limiting oxygen index was 28.5%, and the XPS plate was almost white.
Example 3
285g of methyl octabromoether, 30g of calcium stearate, 15g of brominated epoxy resin, 0.5g of antioxidant 1010 and 0.3g of antioxidant 168 form a composite brominated flame retardant, the thermal decomposition temperature of the composite flame retardant is 230 ℃ and does not change color, the decomposition temperature of 1 wt% of the composite brominated flame retardant is 265 ℃, then 0.3kg of the composite brominated flame retardant, 0.1kg of talcum powder and 19.6kg of general polystyrene are continuously melted and blended in a double screw set, and CO is adopted2The/ethanol/water combined foaming agent is extruded and foamed. The apparent density of the obtained flame-retardant XPS material containing 1.5 percent of composite brominated flame retardant mass fraction is 29.2kg/m3Thermal conductivity coefficient of0.034W/m.k, a compressive strength of 308kPa, a limiting oxygen index of 28.3%, and a white XPS plate.
Example 4
100g of brominated SBS, 100g of methyl octabromoether, 2.5g of calcium stearate, 2.5g of zinc stearate, 4g of TAIC, 0.6g of antioxidant 1010 and 0.4g of antioxidant 168 are mixed into the composite brominated flame retardant, the composite flame retardant does not change color at the temperature of 235 ℃, the decomposition temperature of 1 wt% of the composite brominated flame retardant is 259 ℃, then 0.6kg of the composite brominated flame retardant, 0.3kg of talcum powder and 19.1kg of general polystyrene are continuously melted and blended in a double screw unit, and the freon/ethanol/water combined foaming agent is adopted for extrusion foaming. The apparent density of the obtained flame-retardant XPS material containing 3.0 percent of composite brominated flame retardant mass fraction is 29.0kg/m3The thermal conductivity was 0.034W/m.k, the compressive strength was 297kPa, the limiting oxygen index was 31.6%, and the XPS plate was white.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are possible within the spirit and scope of the appended claims.

Claims (7)

1. The composite brominated flame retardant with high thermal stability is characterized by consisting of one or a mixture of two of brominated SBS and methyl octabromoether, a heat stabilizer, a hydrogen bromide absorbent and an antioxidant.
2. The complex brominated flame retardant with high thermal stability according to claim 1, which is characterized in that the flame retardant is specifically: mixing one or two of brominated SBS and methyl octabromoether to form 100 parts by mass of flame retardant; 0.5-20 parts by mass of heat stabilizer, 0.1-2 parts by mass of antioxidant and 0.1-4 parts by mass of hydrogen bromide absorbent are all blended with 100 parts by mass of the flame retardant to prepare the composite brominated flame retardant with high heat stabilizer.
3. The complex brominated flame retardant of claim 2, wherein the heat stabilizer is one or more of calcium stearate, zinc stearate and barium stearate.
4. The complex brominated flame retardant of claim 2, wherein the hydrogen bromide absorbent is composed of one or more of bisphenol A glycidyl ether, tetrabromobisphenol A glycidyl ether, low molecular weight brominated epoxy resin, tribromophenol glycidyl ether, divinylbenzene, triallyl triazine Trione (TAIC).
5. The complex brominated flame retardant with high thermal stability as claimed in claim 4, wherein the molecular weight of the low molecular weight brominated epoxy resin is 750-900.
6. The complex brominated flame retardant of claim 2, wherein the antioxidant is prepared by mixing 1010 and 168.
7. The high-efficiency flame-retardant polystyrene foam material is characterized by comprising the following specific components in percentage by weight: 0.5-20 parts by mass of the high-thermal-stability composite brominated flame retardant of any one of claims 1-6, 0-5 parts by mass of talcum powder and 100 parts by mass of polystyrene are added with one or a mixture of more of foaming agents of Freon, ethanol, water and carbon dioxide in the process of melt blending to prepare the flame-retardant expanded polystyrene material.
CN202110031101.5A 2021-01-11 2021-01-11 Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof Pending CN112852015A (en)

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CN114479298A (en) * 2022-02-15 2022-05-13 河北五洲开元环保新材料有限公司 Composition for flame-retardant polystyrene foam and preparation method thereof
CN114773670A (en) * 2022-04-25 2022-07-22 北京工商大学 Methyl octabromoether flame-retardant master batch containing multi-component compatilizer and flame-retardant polystyrene foam material thereof
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CN114773671B (en) * 2022-04-25 2023-10-20 北京工商大学 A spray drying preparation method of methyl octabromoether microcapsules and its flame retardant XPS material
CN114773670B (en) * 2022-04-25 2023-11-14 北京工商大学 Methyl octabromoether flame-retardant master batch containing multicomponent compatilizer and flame-retardant polystyrene foam material thereof
CN114805926A (en) * 2022-05-31 2022-07-29 北京工商大学 Methyl octabromoether recrystallization preparation method containing flame-retardant synergist and flame-retardant foamed polystyrene material thereof
CN114805926B (en) * 2022-05-31 2023-05-05 北京工商大学 Methyl octabromoether recrystallization preparation method containing flame retardant synergist and flame retardant foaming polystyrene material thereof
CN115490974A (en) * 2022-09-22 2022-12-20 河南融盛新材料有限公司 Flame-retardant master batch for extruded polystyrene and preparation method thereof
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