CN114479298A - Composition for flame-retardant polystyrene foam and preparation method thereof - Google Patents

Composition for flame-retardant polystyrene foam and preparation method thereof Download PDF

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CN114479298A
CN114479298A CN202210137625.7A CN202210137625A CN114479298A CN 114479298 A CN114479298 A CN 114479298A CN 202210137625 A CN202210137625 A CN 202210137625A CN 114479298 A CN114479298 A CN 114479298A
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polystyrene
flame
parts
brominated
flame retardant
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刘本刚
刘明
潘祥
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Hebei Wuzhou Kaiyuan Environmental Protection New Material Co ltd
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Hebei Wuzhou Kaiyuan Environmental Protection New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/0023—Use of organic additives containing oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/06—CO2, N2 or noble gases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/08—Supercritical fluid
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/06—Polystyrene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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Abstract

The invention provides a composition for flame-retardant polystyrene foam and a preparation method thereof. The composition comprises, by weight, 85-98 parts of polystyrene resin, 0.8-5 parts of a compatibilizer, 2-8 parts of a brominated flame retardant, 0.1-1 part of a combined catalyst and 3-8 parts of a nucleating agent, wherein the compatibilizer is brominated polystyrene. The proper weight proportion in the composition can improve the dispersion of the brominated flame retardant in a polystyrene matrix; but also can improve the action effect of the flame retardant, reduce the emigration of the flame retardant and ensure that the polystyrene foam has excellent flame retardant performance.

Description

Composition for flame-retardant polystyrene foam and preparation method thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a composition for flame-retardant polystyrene foam and a preparation method thereof.
Background
Polystyrene is a general-purpose plastic, has good heat insulation performance and weather resistance, is easy to process and low in price, and the foam product of polystyrene has wide application. However, the chemical structure determines that the polystyrene is inflammable, and the oxygen index is only 18%, so that the application of the polystyrene in the fields of building, transportation and the like has fire hazard. Therefore, it is necessary to add a flame retardant to the polystyrene foam to ensure safety during use.
Commonly used flame retardants are hydroxide flame retardants, phosphorus flame retardants, nitrogen flame retardants and halogen flame retardants. Among them, the halogen flame retardant, especially the polybrominated flame retardant, has the best flame retardant effect. However, bromine-containing flame retardants release harmful gases during operation (e.g., at elevated temperatures), such as polybrominated diphenyl ethers which decompose at elevated temperatures to release polybrominated dibenzo-oxene and polybrominated dibenzofuran, which are considered to be highly toxic carcinogens.
The application of brominated flame retardants is greatly restricted from safety and environmental concerns. Currently, the widespread use of hexabromocyclododecane has been banned. As a substitute for hexabromine-based flame retardants, the use of environmentally friendly octabromine-based flame retardants (octabromoether, octabromothioether) has begun to increase. Octabromine compounds are also used as flame retardants in the production process of polystyrene foam instead of hexabromine, but the flame retardant effect is found to be reduced obviously because the octabromine flame retardants have poor compatibility with polystyrene and are not easy to disperse uniformly in a polystyrene matrix. Therefore, the improvement of the compatibility of the polar octabromine flame retardant and the nonpolar polystyrene two-phase has important significance for improving the flame retardant capability of the polystyrene foam added with the octabromine compound as the flame retardant.
Disclosure of Invention
The object of the present invention is to provide a composition for flame retardant polystyrene foam, by which flame retardant polystyrene foam can be prepared. Polystyrene with low bromination rate is used as a compatibilizer in the foaming process of polystyrene foam to improve the compatibility of the octabromine flame retardant and a polystyrene matrix, and a certain bonding can be generated between the bromine flame retardant and brominated polystyrene or polystyrene molecules by combining a catalyst, so that the dispersion condition of the bromine flame retardant in the polystyrene matrix is obviously improved. The invention also provides a synthesis method of brominated polystyrene and a technical method for preparing polystyrene foam by utilizing the brominated polystyrene, in particular to a composition for flame-retardant polystyrene foam and a preparation method thereof.
Specifically, the invention provides the following technical scheme:
the first aspect of the present invention provides a composition for flame retardant polystyrene foam, comprising, in parts by weight: 85-98 parts of polystyrene resin, 0.8-5 parts of compatibilizer, 2-8 parts of brominated flame retardant, 0.1-1 part of combined catalyst and 3-8 parts of nucleating agent; the compatibilizer is brominated polystyrene.
In the present invention, brominated polystyrene is used as an additive for improving compatibility between a brominated flame retardant (e.g., octabromine flame retardant) and polystyrene. It should be noted that brominated polystyrene can also be found in many conventional polystyrene production formulations, and its bromine content can reach more than 60%, which can act as a flame retardant. However, the flame retardant ability of brominated polystyrene is not very good when it is used, and the compatibility between brominated polystyrene having a high bromine content and a polystyrene resin is poor, so that the flame retardant ability is not very good. In view of this fact, the brominated polystyrene used in the present invention mainly plays a role in improving the compatibility between the brominated flame retardant and the polystyrene matrix, and requires good compatibility with both the brominated flame retardant and the polystyrene, so that the brominated polystyrene is selected in an appropriate content. And simultaneously, a proper content of brominated flame retardant is added to ensure the flame retardant capability of the polystyrene. The provided composition can be used for preparing flame-retardant polystyrene foam and can be used for preparing environment-friendly flame-retardant polystyrene foam.
According to an embodiment of the present invention, the above-described composition for flame-retardant polystyrene foam further comprises the following technical features:
further, the composition comprises 90-94 parts of polystyrene resin, 1-3 parts of a compatibilizer, 3-8 parts of a brominated flame retardant, 0.1-0.8 part of a bonding catalyst and 4-6 parts of a nucleating agent.
Further, the brominated polystyrene is obtained by brominating polystyrene, and the polystyrene is prepared by a living polymerization method.
Further, the polystyrene has a number average molecular weight of 0.8 to 3.0X 104And the polydispersity index of the polystyrene molecular weight is less than or equal to 1.2. The brominated polystyrene with narrow molecular weight distribution is selected, and the compatibility between the brominated flame retardant and the polystyrene matrix can be improved, so that the brominated flame retardant is flame-retardantThe agent or polystyrene has good compatibility.
Further, the bromine content of the brominated polystyrene is 6% -30%.
Further, the brominated flame retardant is selected from at least one of octabromoether and octabromothioether.
Further, the nucleating agent is a granular carbonate.
Further, the nucleating agent is selected from at least one of calcium carbonate, magnesium carbonate and zinc carbonate.
Further, the particle size of the carbonate particles is 500nm-3000 nm. For example, 500nm-2500nm, 1000nm-2500nm, 1500nm-2500nm, 2000nm-2500 nm.
Further, the bound catalyst is a lewis acid.
Further, the Lewis acid is selected from at least one of anhydrous ferric trichloride, anhydrous aluminum trichloride, anhydrous stannic chloride and anhydrous zinc chloride.
A second aspect of the present invention provides a method of making a flame retardant polystyrene foam as described in any of the embodiments of the first aspect, comprising: mixing polystyrene resin, a compatibilizer, a brominated flame retardant, a bonding agent and a nucleating agent, and extruding and foaming to obtain the flame-retardant polystyrene foam.
According to an embodiment of the invention, the method further comprises: extruding and foaming under the action of a supercritical carbon dioxide foaming agent.
In a third aspect of the invention there is provided a flame retardant polystyrene foam prepared according to the method of the second aspect of the invention.
The beneficial effects obtained by the invention are as follows:
the brominated polystyrene with proper content is used as the compatibilizer between the brominated flame retardant and the polystyrene matrix, so that the dispersion condition of the flame retardant in the polystyrene is obviously improved; by adding the bonding catalyst, part of flame retardant molecules can be bonded on polymer molecular chains, so that the aggregation and migration of the flame retardant in a polystyrene matrix are hindered. The invention greatly improves the flame retardant efficiency of the brominated flame retardant in the polystyrene foam, and the provided flame-retardant polystyrene foam shows excellent flame retardant effect.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention. In this context, the contents mentioned are all percentages by weight, unless otherwise specified.
Herein, the polystyrene resin is mentioned as a conventional resin in the art. Which can be obtained by direct purchase on the market. Reference herein to polystyrene is to polystyrene of controlled molecular weight obtained by living polymerization, which can be used to prepare brominated polystyrene. The combined catalyst is a catalyst which can promote a certain bonding between the brominated flame retardant and the brominated polystyrene or polystyrene molecules, so that the dispersion condition of the brominated flame retardant in a polystyrene matrix is obviously improved.
The invention provides a composition for flame-retardant polystyrene foam, which comprises the following components in parts by weight: 85-98 parts of polystyrene resin, 0.8-5 parts of compatibilizer, 2-8 parts of brominated flame retardant, 0.1-1 part of combined catalyst and 3-8 parts of nucleating agent, wherein the solubilizer is brominated polystyrene. The proper weight proportion in the composition can improve the dispersion of the brominated flame retardant in a polystyrene matrix; but also can improve the action effect of the flame retardant, reduce the emigration of the flame retardant and ensure that the polystyrene foam has excellent flame retardant performance.
According to the specific embodiment of the invention, the composition comprises 90-94 parts of polystyrene resin, 1-3 parts of compatibilizer, 3-6 parts of brominated flame retardant, 0.1-0.8 part of bonding catalyst and 4-6 parts of nucleating agent.
According to a particular embodiment, the brominated polystyrene is obtained by bromination of polystyrene, the polystyrene having a number-average molecular weight of 0.8 to 3.0X 104(e.g., 0.8 to 2.5X 104，1.0-2.0×104，1.2-2.0×104，1.2-1.8×104) And the polydispersity index of the polystyrene molecular weight is less than or equal to 1.2. Under the condition ofPolystyrene can be obtained by living polymerization. The mentioned polystyrene living polymerization method includes but is not limited to atom transfer polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT), etc.
Polystyrene can be obtained, for example, by the ATRP (atom transfer polymerization) method. Stirring and complexing copper bromide or copper chloride (240 g in 120-plus) and 4, 4-di-tert-butyl bipyridyl (500 g in 330-plus) at normal temperature, and then adding styrene (25-35kg) and an initiator azobisisobutyronitrile (240 g in 120-plus). And introducing nitrogen for 0.5-1h to remove oxygen in the system, vacuumizing and introducing the nitrogen, and repeating for 4-5 times to ensure that the system is in the nitrogen atmosphere. And then reacting at 100-120 ℃ under stirring to obtain a dark green viscous crude product, stopping heating, cooling a reaction system to room temperature, dissolving the crude product by using a certain amount of tetrahydrofuran, then dripping the solution into methanol, collecting precipitate, and drying in vacuum at 60 ℃ for 24 hours to finally obtain the polystyrene.
Further, for example, polystyrene can also be obtained by a RAFT (reversible addition-fragmentation chain transfer polymerization) method. 1.4-3.3kg of styrene, 120 g of 2, 2-dithiodipropylbispropionyl diurea diacetic acid and 18-34g of azobisisobutyronitrile are dissolved in 25-40L of anhydrous tetrahydrofuran, and the mixture is evacuated and purged with nitrogen and repeated several times to remove oxygen. And then placing the reaction bottle in an oil bath kettle at 70 ℃ for reaction for 8-10h, opening the bottle stopper and exposing the reaction liquid to the air to terminate the reaction. The solvent was removed by evaporation to give the crude product. And precipitating the crude product in ether and evaporating to dryness to obtain the polystyrene.
The above method is used to prepare polystyrene, and then the polystyrene can be brominated to obtain brominated polystyrene. According to a particular embodiment, the brominated polystyrene has a bromine content of 6% to 30%. For example, it may be 10% to 30%, 10% to 20%. Adding 2kg of polystyrene into 17-24L of dichloroethane, stirring until the polystyrene is completely dissolved, then adding 50-70g of antimony trichloride serving as a catalyst into the system, and continuously dissolving for 1-2 hours. Controlling the temperature of the system at 5-15 ℃, dropwise adding 0.8-2.4kg of dichloroethane solution (with the concentration of 50%) of bromine chloride into the system, reacting at 20-30 ℃ for 2-5h, and then treating residual liquid bromine in the system by using sodium sulfite solution with the mass fraction of 8-15% to obtain brominated polystyrene solution. And washing the brominated polystyrene solution by using deionized water and a saturated sodium carbonate solution, and evaporating the solution to dryness to obtain the brominated polystyrene.
According to a specific embodiment, the brominated flame retardant is selected from at least one of octabromoether and octabromothioether.
According to particular embodiments, the nucleating agent is a particulate carbonate salt, including but not limited to calcium carbonate, magnesium carbonate, zinc carbonate, and the like. According to a particular embodiment, the carbonate particles have a particle size of 500nm to 3000 nm. According to a particular embodiment mode, the bound catalyst is a lewis acid; the Lewis acid is at least one selected from anhydrous ferric trichloride, anhydrous aluminum trichloride, anhydrous stannic chloride and anhydrous zinc chloride.
A second aspect of the present invention provides a method of making a flame retardant polystyrene foam as described in any of the embodiments of the first aspect, comprising: mixing polystyrene resin, a compatibilizer, a brominated flame retardant, a bonding agent and a nucleating agent, and extruding and foaming to obtain the flame-retardant polystyrene foam.
According to an embodiment of the invention, the method further comprises: extruding and foaming under the action of a supercritical carbon dioxide foaming agent.
According to the specific embodiment of the invention, polystyrene resin, brominated polystyrene, a brominated flame retardant, a combined catalyst and a nucleating agent are respectively and simultaneously added into a double-screw extruder for plasticization through a weight loss counter, and are extruded and foamed into the flame-retardant PS foam after being uniformly mixed with a foaming agent. The temperature settings of the extruder were as follows: the first temperature is 165 ℃, the second temperature is 195 ℃, the third temperature is 210 ℃, the fourth temperature is 190 ℃ and the die temperature is 150 ℃. The rotating speed is 30-50r/min, and the traction speed is 2 m/min. In the plasticizing process, Friedel-Crafts reaction is carried out between octabromoether/octabromothioether and brominated styrene or styrene through a catalytic binding agent, and flame retardant molecules are bonded on a high molecular chain by sacrificing a small amount of bromine elements. Polystyrene and octabromoether bonding are exemplified below.
Figure BDA0003505600520000051
In a third aspect of the invention there is provided a flame retardant polystyrene foam prepared according to the method of the second aspect of the invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Example 1 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
214g of copper chloride and 860g of 4, 4-di-tert-butyl bipyridine are stirred and complexed at normal temperature, and then 30kg of styrene and 262g of azobisisobutyronitrile are added and stirred to dissolve. And introducing nitrogen into the system for 1h to remove oxygen in the system, vacuumizing and introducing the nitrogen again, and repeating for 4-5 times to ensure that the system is protected under the nitrogen atmosphere. The reaction was then stirred at 105 ℃ for 7h to give the crude product. Dissolving the crude product with tetrahydrofuran, dripping the solution into methanol, collecting precipitate, and drying to obtain polystyrene product Mn＝0.88×104Coefficient of molecular weight distribution Mw/Mn＝1.17。
(2) Synthesis of brominated polystyrene
2kg of polystyrene is added into 22L of dichloroethane and stirred until the polystyrene is completely dissolved, and then 60g of catalyst antimony trichloride is added into the mixture and the dissolution is continued for 1 to 2 hours. Controlling the temperature of the system at 5-15 ℃, dropwise adding 1.2kg of dichloroethane solution (with the concentration of 50%) of bromine chloride into the system, reacting at 20-30 ℃ for 4h, and then treating residual liquid bromine in the system by using sodium sulfite solution with the concentration of 10% to obtain brominated polystyrene solution. And washing the brominated polystyrene solution by using deionized water and a saturated sodium carbonate solution, and evaporating the solution to dryness to obtain a brominated polystyrene product. The bromine content of the brominated polystyrene was found to be 22.5%.
(3) Preparation of flame-retardant polystyrene foam
9kg of polystyrene resin, 0.15kg of brominated polystyrene, 0.38kg of octabromoether, 0.05kg of anhydrous zinc chloride and 0.45kg of calcium carbonate are respectively and simultaneously added into a double-screw extruder through a weight loss counter for plasticizing, and are extruded and foamed after being uniformly mixed with a foaming agent to obtain the flame-retardant polystyrene foam. Wherein the temperature of the first section is 165 ℃, the temperature of the second section is 195 ℃, the temperature of the third section is 210 ℃, the temperature of the fourth section is 190 ℃ and the temperature of the die orifice is 150 ℃. The rotating speed is 50r/min, and the traction speed is 2 m/min.
The flame retardant polystyrene foam prepared in example 1 was numbered IPS-1.
Example 2
Example 2 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
357g of copper bromide and 860g of 4, 4-di-tert-butyl bipyridine are stirred and complexed at normal temperature, and then 45kg of styrene and 450g of azobisisobutyronitrile are added and stirred to dissolve. Introducing nitrogen into the system for 0.5-1h to remove oxygen in the system, then vacuumizing and introducing nitrogen, and repeating for 4-5 times to ensure that the system is protected by the nitrogen atmosphere. The reaction was then stirred at 110 ℃ for 12h to give the crude product. Dissolving the crude product with tetrahydrofuran, dripping the solution into methanol, collecting precipitate, and drying to obtain polystyrene product Mn＝1.32×104Coefficient of molecular weight distribution Mw/Mn＝1.11。
(2) Synthesis of brominated polystyrene
2kg of polystyrene is added into 25L of dichloroethane and stirred until the polystyrene is completely dissolved, and then 60g of catalyst antimony trichloride is added into the dichloroethane and the dissolution is continued for 1 to 2 hours. And (3) controlling the temperature of the system to be 5-15 ℃, dropwise adding 1.0kg (with the concentration of 50%) of dichloroethane solution of bromine chloride into the system, reacting for 3 hours at 20-30 ℃, and then treating residual liquid bromine in the system by using sodium sulfite solution with the mass fraction of 8% to obtain brominated polystyrene solution. And washing the brominated polystyrene solution by using deionized water and a saturated sodium carbonate solution, and evaporating the solution to dryness to obtain a brominated polystyrene product. The bromine content of the brominated polystyrene was found to be 14.5%.
(3) Preparation of flame-retardant polystyrene foam
Using the brominated polystyrene described above, a flame retardant polystyrene foam was prepared according to the method of example 1.
The flame retardant polystyrene foam prepared in example 2 was numbered IPS-2.
Example 3
Example 3 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
2kg of styrene, 164g of 2, 2-dithiodipropylbisiloyldiauryldiphenyldiacetic acid and 20g of azobisisobutyronitrile were dissolved in 25L of anhydrous tetrahydrofuran, and the mixture was evacuated and purged with nitrogen several times to remove oxygen. Then the reaction flask is placed in an oil bath kettle at 70 ℃ for reaction for 10h, and the bottle stopper is opened to expose the reaction liquid to the air to stop the reaction. The solvent was removed by evaporation to give the crude product. The crude product is precipitated in ether and evaporated to dryness to obtain polystyrene. M thereofn＝1.58×104Molecular weight distribution coefficient Mw/Mn＝1.17。
(2) Synthesis of brominated polystyrene
Brominated polystyrene was synthesized by referring to the method in example 2, and the bromine content of the prepared brominated polystyrene was measured to be 15.6%.
(3) Preparation of flame-retardant polystyrene foam
The brominated polystyrene used was the brominated polystyrene prepared in example 3, and the synthesis was the same as in example 1.
Example 3 the flame retardant polystyrene foam prepared was numbered IPS-3.
Example 4
Example 4 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
Polystyrene was synthesized according to the method of example 2.
(2) Synthesis of brominated polystyrene
Brominated polystyrene was synthesized according to the method of example 2.
(3) Preparation of flame-retardant polystyrene foam
9kg of polystyrene resin, 0.15kg of brominated polystyrene, 0.38kg of octabromothioether, 0.05kg of anhydrous zinc chloride and 0.45kg of calcium carbonate are respectively and simultaneously added into a double-screw extruder through a weight loss counter for plasticizing, and then added with a supercritical carbon dioxide foaming agent, and the mixture is extruded and foamed into the flame-retardant polystyrene foam after being uniformly mixed. Wherein the temperature settings of the extruder were as follows: one section is 165 ℃, the second section is 195 ℃, the third section is 210 ℃, the fourth section is 190 ℃, and the die orifice is 150 ℃. The rotating speed is 50r/min, and the traction speed is 2 m/min.
The number of the prepared flame-retardant polystyrene foam is IPS-4.
Example 5
Example 5 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
Polystyrene was synthesized according to the method of example 2.
(2) Synthesis of brominated polystyrene
Brominated polystyrene was synthesized according to the method of example 2.
(3) Preparation of flame-retardant polystyrene foam
9kg of polystyrene resin, 0.15kg of brominated polystyrene, 0.38kg of octabromothioether, 0.03kg of anhydrous ferric chloride and 0.48kg of calcium carbonate are respectively and simultaneously added into a double-screw extruder through a weight loss counter for plasticizing, and then added with a supercritical carbon dioxide foaming agent, and the mixture is extruded and foamed into the flame-retardant PS foam after being uniformly mixed. Wherein the temperature settings of the extruder were as follows: one section is 165 ℃, the second section is 195 ℃, the third section is 210 ℃, the fourth section is 190 ℃, and the die orifice is 150 ℃. The rotating speed is 50r/min, and the traction speed is 2 m/min.
The number of the prepared flame-retardant polystyrene foam is IPS-5.
Example 6
Example 6 a synthetic flame retardant polystyrene foam was prepared as follows.
(1) Synthetic polystyrene
Polystyrene was synthesized according to the method of example 2.
(2) Synthesis of brominated polystyrene
The synthesis method is the same as example 2.
(3) Preparation of flame-retardant polystyrene foam
9kg of polystyrene resin, 0.18kg of brominated polystyrene, 0.5kg of octabromoether, 0.030g of anhydrous ferric chloride and 0.48kg of calcium carbonate are respectively and simultaneously added into a double-screw extruder through a weightlessness counter for plasticizing, and added with a supercritical carbon dioxide foaming agent, and the mixture is extruded and foamed into the flame-retardant PS foam after being uniformly mixed. The temperature settings of the extruder were as follows: one section is 165 ℃, the second section is 195 ℃, the third section is 210 ℃, the fourth section is 190 ℃, and the die orifice is 150 ℃. The rotating speed is 50r/min, and the traction speed is 2 m/min.
The number of the prepared flame-retardant polystyrene foam is IPS-6.
Example 7
Example 7 the flame retardant polystyrene foam prepared as described above was tested.
Testing of the combustion properties of the foams:
according to three standards of GB/T8626 'flammability test method of building materials', GB/T20284 'monomer burning test of building materials or products', GB/T5464 'non-flammability test method of building materials', the prepared flame-retardant polystyrene foam is subjected to burning performance test, and the results are as follows:
TABLE 1 Combustion Properties of flame-retardant polystyrene foams
Figure BDA0003505600520000081
Figure BDA0003505600520000091
From the results given above, referring to the standard "fire performance grading of building materials and products" (GB8624-2012), the fire retardant performance of each sample reaches the fire performance index above B2.
According to the results, the brominated polystyrene in the embodiment 2 and the embodiment 3 has a better using effect, which shows that the higher the bromine content in the brominated polystyrene is, the more favorable the flame retardant property of the polystyrene is, and the more important the brominated polystyrene has the capability of improving the compatibility between the flame retardant and the polystyrene; although IPS-3 performs better than IPS-2, its use of large amounts of solvent in the preparation of brominated polystyrene is not conducive to scale-up.
Compared with IPS-4 and IPS-2, the flame retardant adopts octabromoether or octabromothioether, and the flame retardant performance is basically not influenced. When the flame retardant amount in the formula reaches 4.5 wt%, the flame retardant property of the polystyrene foam reaches the standard of B1 (IPS-6), and the polystyrene foam shows excellent flame retardant property.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A composition for flame retardant polystyrene foam, comprising, in parts by weight:
85-98 parts of polystyrene resin, preferably 90-94 parts,
0.8 to 5 parts of compatibilizer, preferably 1 to 3 parts,
2-8 parts of bromine flame retardant, preferably 3-8 parts,
bound catalyst 0.1-1 parts, preferably 0.1-0.8 parts, and
3-8 parts of nucleating agent, preferably 4-6 parts;
the compatibilizer is brominated polystyrene.
2. The composition for flame retarded polystyrene foam according to claim 1, wherein said brominated polystyrene is obtained by bromination of polystyrene, said polystyrene being obtained by a living polymerization process.
3. The composition for flame-retardant polystyrene foam according to claim 1, wherein the polystyrene has a number average molecular weight of 0.8 to 3.0 x 104And the polydispersity index of the polystyrene molecular weight is less than or equal to 1.2.
4. The composition for flame retarded polystyrene foam according to claim 1, wherein the brominated polystyrene has a bromine content of 6% to 30%.
5. The composition for flame retarding polystyrene foam according to claim 1, wherein the brominated flame retardant is selected from at least one of octabromoether and octabromothioether.
6. The composition for flame retarded polystyrene foam according to claim 1, wherein said nucleating agent is a carbonate in particulate form;
optionally, the nucleating agent is selected from at least one of calcium carbonate, magnesium carbonate and zinc carbonate;
optionally, the carbonate particles have a particle size of 500nm to 3000 nm.
7. The composition for flame retarded polystyrene foam according to claim 1, wherein said bound catalyst is a lewis acid;
optionally, the Lewis acid is selected from at least one of anhydrous ferric trichloride, anhydrous aluminum trichloride, anhydrous stannic tetrachloride and anhydrous zinc chloride.
8. A method of making the flame retarded polystyrene foam of any one of claims 1 to 7, comprising:
mixing polystyrene resin, a compatibilizer, a brominated flame retardant, a bonding agent and a nucleating agent, and extruding and foaming to obtain the flame-retardant polystyrene foam.
9. The method of claim 8, further comprising: extruding and foaming under the action of a supercritical carbon dioxide foaming agent.
10. A flame-retardant polystyrene foam, characterized in that it is obtained by the process according to claims 8 to 9.
CN202210137625.7A 2022-02-15 2022-02-15 Composition for flame-retardant polystyrene foam and preparation method thereof Pending CN114479298A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966567A (en) * 2006-11-24 2007-05-23 北京理工大学 Flame-proof polystyrene composition and its preparation method
CN112852015A (en) * 2021-01-11 2021-05-28 北京工商大学 Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof
CN113896822A (en) * 2021-11-12 2022-01-07 南京越升挤出机械有限公司 Preparation method of high-efficiency flame-retardant polystyrene by applying bromine flame retardant containing active functional group

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1966567A (en) * 2006-11-24 2007-05-23 北京理工大学 Flame-proof polystyrene composition and its preparation method
CN112852015A (en) * 2021-01-11 2021-05-28 北京工商大学 Composite brominated flame retardant with high thermal stability and efficient flame-retardant polystyrene foam material thereof
CN113896822A (en) * 2021-11-12 2022-01-07 南京越升挤出机械有限公司 Preparation method of high-efficiency flame-retardant polystyrene by applying bromine flame retardant containing active functional group

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