Organic phosphorus modified aluminum hydroxide flame-retardant polystyrene plastic and preparation method thereof

Abstract

The invention relates to the technical field of flame retardance, and discloses an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic, which is characterized in that under the photo-initiation action of 2-hydroxy-2-methylphenylpropane-1-ketone, sulfydryl introduced on the surface of aluminum hydroxide and alkenyl of acryloyloxy bis-spiro phosphate are subjected to efficient and rapid click reaction, so that the flame-retardant property of the polystyrene plastic is improved, and the flame-retardant property of the polystyrene plastic is improved. The preparation method comprises the following steps: preparing a bis-spirocyclic phosphate compound, chemically grafting the bis-spirocyclic phosphate compound to the surface of aluminum hydroxide through a novel chemical synthesis method to obtain organophosphorus modified aluminum hydroxide, applying the organophosphorus modified aluminum hydroxide as an organic-inorganic synergistic flame retardant to polystyrene plastic, and preparing the bis-spirocyclic phosphate compound grafted to the surface of the aluminum hydroxide at a high temperature. The modified polystyrene material can be decomposed to generate an oxygen-containing phosphate compound, and the oxygen-containing phosphate compound is compounded with aluminum hydroxide, so that the modified polystyrene material has good effects of absorbing water, promoting char formation and inhibiting a combustion reaction process, the limit oxygen index of the polystyrene material is remarkably improved, and an excellent natural effect is shown.

Description

Technical Field

[0001] The invention relates to the technical field of flame retardancy, in particular to an organophosphorus-modified aluminum hydroxide flame retardant polystyrene plastic and a preparation method thereof. Background Art

[0002] Flame retardants can enhance the flame retardant properties of plastics, rubber and other materials. Common flame retardants include aluminum hydroxide, antimony trioxide, phosphorus-containing flame retardants, etc. Among them, aluminum hydroxide, as an inorganic flame retardant, is non-toxic and pollution-free, has good chemical stability, and has flame retardant and smoke suppression effects. It is widely used in polymer materials. However, the flame retardancy of a single aluminum hydroxide is not high. Aluminum hydroxide is usually compounded with red phosphorus, melamine phosphate, etc. to achieve a flame retardant effect. Therefore, the organophosphorus flame retardant can be chemically grafted onto the surface of aluminum hydroxide to obtain an organic-inorganic composite flame retardant.

[0003] Polystyrene is a common polymer material with excellent thermal stability, insulation and light stability. It is widely used in packaging film materials, containers and utensils, optical and chemical instrument parts, etc. However, traditional polystyrene is not flame retardant and is easy to burn. A single aluminum hydroxide flame retardant is difficult to effectively enhance the flame retardancy of polystyrene. Therefore, organophosphorus flame retardants and aluminum hydroxide can be organically combined to synergistically flame retard polystyrene. Summary of the invention

[0004] In view of the deficiencies in the prior art, the present invention provides an organophosphorus modified aluminum hydroxide flame retardant polystyrene plastic and a preparation method thereof, which organically combines the organophosphorus flame retardant and aluminum hydroxide to significantly enhance the flame retardancy of polystyrene.

[0005] To achieve the above object, the present invention provides the following technical solution: an organophosphorus-modified aluminum hydroxide flame-retardant polystyrene plastic, and a preparation method of the organophosphorus-modified aluminum hydroxide flame-retardant polystyrene plastic is as follows: (1) Add nano aluminum hydroxide and mercaptopropylmethyldimethoxysilane to an ethanol solvent, disperse them uniformly by ultrasonication, heat to 40-70 °C, react for 2-6 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0006] (2) Add mercapto-modified aluminum hydroxide and acryloxy bispirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then added with a photoinitiator 2-hydroxy-2-methylphenylpropane-1-one to react. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in sequence and dried to obtain an organophosphorus-modified aluminum hydroxide.

[0007] (3) Add polystyrene masterbatch, organophosphorus modified aluminum hydroxide and antioxidant 1076 into a high-speed mixer and mix them evenly. Then place the materials into a twin-screw extruder, melt-mix them at 170-180°C, and then extrude the masterbatch at 180-190°C to obtain organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic.

[0008] Preferably, the mass fractions of ethanol in step (1) are 2500-6000 parts, nano-aluminum hydroxide is 100 parts, and mercaptopropylmethyldimethoxysilane is 6-20 parts.

[0009] Preferably, in step (2), the mass fractions of mercapto-modified aluminum hydroxide are 100 parts, the mass fractions of acryloxybisspirocyclic phosphate are 35-120 parts, and the mass fractions of 2-hydroxy-2-methylphenylpropane-1-one are 0.5-2 parts.

[0010] Preferably, the reaction in step (2) is carried out under ultraviolet light at 35-60° C. for 3-8 h.

[0011] Preferably, the mass fractions of the polystyrene masterbatch in step (3) are 100 parts, and the mass fractions of the organophosphorus-modified aluminum hydroxide are 3-10 parts.

[0012] Compared with the prior art, the present invention has the following beneficial technical effects: The organophosphorus-modified aluminum hydroxide flame-retardant polystyrene plastic comprises: nano aluminum hydroxide surface modified by mercaptopropylmethyldimethoxysilane; under the light initiation of 2-hydroxy-2-methylphenylpropane-1-one, the mercapto group introduced on the surface of the aluminum hydroxide and the alkenyl group of the acryloxy bispirocyclic phosphate undergo an efficient and rapid click reaction, thereby chemically grafting the bispirocyclic phosphate compound onto the surface of the aluminum hydroxide through a new chemical synthesis method to obtain the organophosphorus-modified aluminum hydroxide; the organophosphorus-modified aluminum hydroxide is used as an organic-inorganic synergistic flame retardant to be applied to polystyrene plastic; the bispirocyclic phosphate compound grafted onto the surface of the aluminum hydroxide can be decomposed to generate oxygen-containing phosphate compounds at high temperature; the bispirocyclic phosphate compound is compounded with the aluminum hydroxide to have good water absorption and carbonization promotion effects, can isolate oxygen and inhibit the combustion reaction process, significantly improves the limiting oxygen index and residual carbon rate of the polystyrene material, and exhibits an excellent natural effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is an acryloyloxy bispirocyclic phosphate (C9H 13 O6P). DETAILED DESCRIPTION

[0014] To achieve the above object, the present invention provides the following implementation modes and examples: A method for preparing an organophosphorus-modified aluminum hydroxide flame-retardant polystyrene plastic is as follows: (1) Add 100 parts of nano-aluminum hydroxide and 6-20 parts of mercaptopropylmethyldimethoxysilane to 2500-6000 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 40-70°C, react for 2-6 hours, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0015] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 35-120 parts by weight of acryloxy bispirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 0.5-2 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 35-60 ° C for 3-8 hours under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus modified aluminum hydroxide.

[0016] (3) Add 100 parts by weight of polystyrene masterbatch, 3-10 parts by weight of organophosphorus modified aluminum hydroxide, and 0.2-1 part by weight of antioxidant 1076 into a high-speed mixer and mix them evenly. Then, place the materials in a twin-screw extruder, melt-mix them at 170-180°C, and then extrude the masterbatch at 180-190°C to obtain organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic.

[0017] The organophosphorus modified aluminum hydroxide flame retardant polystyrene plastic was made into a standard specimen of 20 mm×5 mm×5 mm. According to the test method of GB / T 2406.1-2008, the limiting oxygen index was tested using an oxygen index tester with the maximum test temperature of 800 ℃ and the heating rate of 10 ℃ / min. Example 1

[0018] (1) Add 100 parts of nano-aluminum hydroxide and 6 parts of mercaptopropylmethyldimethoxysilane to 2500 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 40 °C, react for 2 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0019] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 35 parts by weight of acryloxybis-spirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 0.5 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 35 ° C for 3 h under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus-modified aluminum hydroxide.

[0020] (3) 100 parts by weight of polystyrene masterbatch, 3 parts by weight of organophosphorus modified aluminum hydroxide, and 0.2 parts by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 170 °C. The masterbatch was then extruded at 185 °C to obtain an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 26.7% and a residual carbon rate of 8.7%. Example 2

[0021] (1) Add 100 parts of nano-aluminum hydroxide and 9 parts of mercaptopropylmethyldimethoxysilane to 3200 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 60 °C, react for 2 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0022] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 50 parts by weight of acryloxybis-spirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 0.8 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 40 ° C for 8 h under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus-modified aluminum hydroxide.

[0023] (3) 100 parts by weight of polystyrene masterbatch, 5 parts by weight of organophosphorus modified aluminum hydroxide, and 0.4 parts by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 175°C. The masterbatch was then extruded at 180°C to obtain an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 27.5% and a residual carbon rate of 10.7%. Example 3

[0024] (1) Add 100 parts of nano-aluminum hydroxide and 12 parts of mercaptopropylmethyldimethoxysilane to 4200 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 60 °C, react for 6 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0025] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 80 parts by weight of acryloxybis-spirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 1.2 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 50 ° C for 5 h under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus-modified aluminum hydroxide.

[0026] (3) 100 parts by weight of polystyrene masterbatch, 6 parts by weight of organophosphorus modified aluminum hydroxide, and 0.6 parts by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 175°C. The masterbatch was then extruded at 185°C to obtain an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 28.8% and a residual carbon rate of 14.1%. Example 4

[0027] (1) Add 100 parts of nano-aluminum hydroxide and 17 parts of mercaptopropylmethyldimethoxysilane to 5000 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 60 °C, react for 6 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0028] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 100 parts by weight of acryloxybis-spirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 1.6 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 50 ° C for 6 h under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus-modified aluminum hydroxide.

[0029] (3) 100 parts by weight of polystyrene masterbatch, 8 parts by weight of organophosphorus modified aluminum hydroxide, and 0.8 parts by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 175°C. The masterbatch was then extruded at 185°C to obtain an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 28.1% and a residual carbon rate of 17.8%. Example 5

[0030] (1) Add 100 parts of nano-aluminum hydroxide and 20 parts of mercaptopropylmethyldimethoxysilane to 6000 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 70 °C, react for 6 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0031] (2) Add 100 parts by weight of mercapto-modified aluminum hydroxide and 120 parts by weight of acryloxy bispirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed evenly, and then 2 parts of photoinitiator 2-hydroxy-2-methylphenylpropane-1-one were added, and the reaction was carried out at 60 ° C for 8 h under ultraviolet light. After the reaction, the solvent was filtered, and the mixture was washed with acetone and ethanol in turn and dried to obtain organophosphorus-modified aluminum hydroxide.

[0032] (3) 100 parts by weight of polystyrene masterbatch, 10 parts by weight of organophosphorus modified aluminum hydroxide, and 1 part by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 180°C. The masterbatch was then extruded at 190°C to obtain an organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 27.3% and a residual carbon rate of 18.4%.

[0033] Comparative Example 1 (1) Add 100 parts of nano-aluminum hydroxide and 10 parts of mercaptopropylmethyldimethoxysilane to 3500 parts of ethanol solvent, disperse them uniformly by ultrasonication, heat to 50 °C, react for 6 h, filter the solvent, wash with ethanol and dry to obtain mercapto-modified aluminum hydroxide.

[0034] (2) 100 parts by weight of polystyrene masterbatch, 6 parts by weight of mercapto-modified aluminum hydroxide, and 0.4 parts by weight of antioxidant 1076 were added into a high-speed mixer and mixed evenly. The materials were then placed into a twin-screw extruder and melt-mixed at 170 °C. The masterbatch was then extruded at 185 °C to obtain an organophosphorus-modified aluminum hydroxide flame-retardant polystyrene plastic having a limiting oxygen index of 27.3% and a residual carbon rate of 18.4%.

Claims

1. An organophosphorus modified aluminum hydroxide flame retardant polystyrene plastic, characterized in that: The preparation method of the organophosphorus modified aluminum hydroxide flame retardant polystyrene plastic is as follows: (1) Adding nano aluminum hydroxide and mercaptopropylmethyldimethoxysilane to an ethanol solvent, uniformly dispersing by ultrasonication, heating to 40-70°C, reacting for 2-6 hours, filtering the solvent, washing with ethanol and drying to obtain mercapto-modified aluminum hydroxide; (2) Add mercapto-modified aluminum hydroxide and acryloxy bispirocyclic phosphate (C9H 13 O6P), ultrasonically dispersed uniformly, then added with photoinitiator 2-hydroxy-2-methylphenylpropane-1-one, reacted, filtered the solvent after the reaction, washed with acetone and ethanol in sequence and dried, to obtain organophosphorus modified aluminum hydroxide; (3) Add polystyrene masterbatch, organophosphorus modified aluminum hydroxide and antioxidant 1076 into a high-speed mixer and mix them evenly. Then place the materials into a twin-screw extruder, melt-mix them at 170-180°C, and then extrude the masterbatch at 180-190°C to obtain organophosphorus modified aluminum hydroxide flame-retardant polystyrene plastic.

2. The organic phosphorus modified aluminum hydroxide flame retardant polystyrene plastic according to claim 1, characterized in that: The mass fractions of ethanol in step (1) are 2500-6000 parts, nano-aluminum hydroxide is 100 parts, and mercaptopropylmethyldimethoxysilane is 6-20 parts.

3. The organic phosphorus modified aluminum hydroxide flame retardant polystyrene plastic according to claim 1, characterized in that: The mass fractions of mercapto-modified aluminum hydroxide in step (2) are 100 parts, acryloxy bispirocyclic phosphate is 35-120 parts, and 2-hydroxy-2-methylphenylpropane-1-one is 0.5-2 parts.

4. The organic phosphorus modified aluminum hydroxide flame retardant polystyrene plastic according to claim 1, characterized in that: The reaction in step (2) is carried out at 35-60° C. for 3-8 h under ultraviolet light.

5. The organic phosphorus modified aluminum hydroxide flame retardant polystyrene plastic according to claim 1, characterized in that: The mass fractions of the polystyrene masterbatch in step (3) are 100 parts, and the mass fractions of the organophosphorus-modified aluminum hydroxide are 3-10 parts.

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