Reactive graphene flame-retardant modified polystyrene plastic and preparation method thereof

Abstract

The invention relates to the technical field of flame retardance, and discloses a reaction type graphene flame-retardant modified polystyrene plastic, acryloyloxy diethyl phosphate of graphene and styrene are polymerized to obtain reaction type graphene grafted polystyrene, and then the reaction type graphene grafted polystyrene is compounded with impact polystyrene to obtain the reaction type graphene flame-retardant modified polystyrene plastic. The reaction type graphene flame-retardant modified polystyrene plastic is obtained, acryloyloxy diethyl phosphate bonded on the surface of graphene serves as a reaction type flame retardant and is subjected to graft polymerization with styrene, graphene and polystyrene have higher interface bonding force, compatibility of the graphene and the polystyrene is better, and the reaction type graphene flame-retardant modified polystyrene plastic is obtained. According to the present invention, the influence of the reaction type graphene on the use performance of the polystyrene is avoided, the acryloyloxy diethyl phosphate small molecules on the surface of the graphene are adopted as the phosphorus-containing flame retardant, can be decomposed during combustion to produce the phosphoric acid compound, can promote the water absorption carbonization, and can be compounded with the graphene to form the continuous carbon barrier layer so as to achieve the good synergistic flame retardation effect;

Description

Technical Field

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

[0002] Graphene has a unique two-dimensional honeycomb sheet structure and excellent mechanical, thermal and electrical properties. It has broad application prospects in polymer materials, electrochemical energy, biomedicine, etc. Patent CN201610860181.4 "Preparation method of flame-retardant water-based polyurethane based on reactive graphene flame retardant" discloses the introduction of hydroxyl groups on the surface of graphene as a reactive flame retardant, which is grafted and polymerized with polyurethane, giving the polyurethane excellent wear resistance, high temperature resistance and synergistic flame retardant effects.

[0003] Reactive flame retardants participate in the polymerization reaction as polymerization monomers. The polymer itself also has flame retardant components, which has little effect on the performance of polymer materials and has long-lasting flame retardancy. Therefore, reactive phosphorus-containing flame retardants can be introduced on the surface of graphene and grafted with polymer materials such as polystyrene and polyurethane to obtain flame-retardant polymer materials. Summary of the invention

[0004] 1. Technical issues to be resolved In view of the deficiencies in the prior art, the present invention provides a reactive graphene flame retardant modified polystyrene plastic and a preparation method thereof, thereby improving the flame retardant properties of the polystyrene plastic.

[0005] (II) Technical solution To achieve the above object, the present invention provides the following technical solution: a reactive graphene flame retardant modified polystyrene plastic, the preparation method of which is as follows: (1) Add graphene oxide to thionyl chloride, heat to 55-70 °C and treat for 12-24 h to obtain graphene chloride.

[0006] (2) Add acylated graphene and diethyl bis(2-hydroxyethyl) phosphate into acetone solvent, disperse them evenly, then add catalyst triethylamine dropwise, react at 10-30 °C for 5-20 h, filter and wash with acetone after the reaction, and obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0007] (3) Add hydroxyethyl diethyl phosphate modified graphene, acrylic acid or methacrylic acid to ethyl acetate, dropwise add catalyst 4-dimethylaminopyridine and condensation agent dicyclohexylcarbodiimide to react, filter after the reaction, wash with ethyl acetate and acetone to obtain acryloxy diethyl phosphate modified graphene.

[0008] (4) Add 15-40 parts by weight of acryloxy diethyl phosphate modified graphene, 100 parts of styrene and 0.12-0.18 parts of polyvinyl alcohol into deionized water and stir evenly, then dropwise add 1.5-2.5 parts of dibenzoyl peroxide, heat to cause polymerization reaction, filter after the reaction, and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0009] (5) Reactive graphene grafted polystyrene, high impact polystyrene, plasticizer dioctyl phthalate, and lubricant ethylene bisstearamide are uniformly blended in a high-speed mixer, and then the mixture is melted and extruded in a twin-screw extruder at 180-210 °C to obtain reactive graphene flame retardant modified polystyrene plastic.

[0010] Preferably, in step (2), the amounts of the graphene chloride, diethyl bis(2-hydroxyethyl)phosphate and triethylamine are 100 parts by weight, 30-120 parts by weight and 8-30 parts by weight.

[0011] Preferably, the reaction in step (3) is carried out at 20-50°C for 6-24 hours. Preferably, in step (3), the weight percentages are as follows: 100 parts of hydroxyethyl diethyl phosphate modified graphene, 18-80 parts of acrylic acid, 1.5-6 parts of 4-dimethylaminopyridine, and 35-150 parts of condensation agent dicyclohexylcarbodiimide.

[0012] Preferably, the reaction in step (4) is carried out at 75-90° C. for 2-6 h.

[0013] Preferably, in step (5), the reactive graphene grafted polystyrene is 2-10 parts and the high impact polystyrene is 100 parts by weight.

[0014] 3. Beneficial technical effects Compared with the prior art, the present invention has the following beneficial technical effects: The reactive graphene flame retardant modified polystyrene plastic comprises a phosphorus-containing flame retardant, wherein a hydroxyl group of bis(2-hydroxyethyl) diethyl phosphate undergoes an esterification reaction with an acyl chloride group on the surface of graphene to obtain hydroxyethyl diethyl phosphate modified graphene, and then under the catalysis of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, the hydroxyl group of hydroxyethyl diethyl phosphate reacts with acrylic acid to generate an acryloyloxy functional group to obtain acryloyloxy diethyl phosphate modified graphene, thereby introducing polymerizable acryloyloxy diethyl phosphate small molecules on the surface of graphene, and under the initiation of dibenzoyl peroxide, the acryloyloxy diethyl phosphate of the graphene is polymerized with styrene to obtain the reactive graphene. Graphene is grafted onto polystyrene, and then compounded with high-impact polystyrene to obtain reactive graphene flame-retardant modified polystyrene plastic. The acryloxy diethyl phosphate bonded to the surface of graphene serves as a reactive flame retardant and is grafted and polymerized with styrene. There is a stronger interface bonding force between graphene and polystyrene, and the two have better compatibility, thereby avoiding the influence of reactive graphene on the performance of polystyrene. The small molecules of acryloxy diethyl phosphate on the surface of graphene serve as phosphorus-containing flame retardants, which decompose during combustion to produce phosphoric acid compounds, which can promote water absorption and carbonization, and are compounded with graphene to form a continuous carbon barrier layer, which has a better synergistic flame retardant effect and gives polystyrene excellent flame retardant properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is the structural formula of diethyl bis(2-hydroxyethyl) phosphate; Figure 2 It is a schematic diagram of the structure of graphene modified with diethyl hydroxyethyl phosphate; Figure 3 This is a schematic diagram of the structure of acryloxy diethyl phosphate modified graphene.

[0016] Figure 4 It is a peak test graph of heat release rate of the embodiment and the comparative example.

[0017] Figure 5 It is a test chart of total heat release of the embodiment and the comparative example. DETAILED DESCRIPTION

[0018] To achieve the above object, the present invention provides the following implementation modes and examples: A reactive graphene flame retardant modified polystyrene plastic, the preparation method of which is as follows: (1) Add graphene oxide to thionyl chloride, heat to 55-70 °C and treat for 12-24 h to obtain graphene chloride.

[0019] (2) Add 100 parts by weight of acylated graphene chloride and 30-120 parts by weight of diethyl bis(2-hydroxyethyl) phosphate into acetone solvent, disperse them evenly, then drop 8-30 parts of catalyst triethylamine, react at 10-30°C for 5-20 hours, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0020] (3) Add 100 parts by weight of hydroxyethyl diethyl phosphate modified graphene and 18-80 parts by weight of acrylic acid or methacrylic acid to ethyl acetate, add dropwise 1.5-6 parts of catalyst 4-dimethylaminopyridine and 35-150 parts of condensation agent dicyclohexylcarbodiimide, react at 20-50 °C for 6-24 h, filter after the reaction, wash with ethyl acetate and acetone, and obtain acryloxy diethyl phosphate modified graphene.

[0021] (4) Add 15-40 parts by weight of acryloxy diethyl phosphate modified graphene, 100 parts of styrene and 0.12-0.18 parts of polyvinyl alcohol into deionized water and stir evenly, then dropwise add 1.5-2.5 parts of dibenzoyl peroxide, raise the temperature to 75-90 °C to allow polymerization reaction for 2-6 hours, filter after the reaction, and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0022] (5) 2-10 parts by weight of reactive graphene grafted polystyrene, 100 parts of impact polystyrene, a plasticizer of dioctyl phthalate, and a lubricant of ethylene bisstearamide are uniformly blended in a high-speed mixer, and then the mixture is melted and extruded in a twin-screw extruder at 180-210° C. to obtain a reactive graphene flame retardant modified polystyrene plastic. Example 1

[0023] (1) Add 0.2 g of graphene oxide to 10 mL of thionyl chloride, heat to 55 °C and treat for 12 h to obtain graphene chloride.

[0024] (2) Add 0.5 g of acyl chloride graphene and 0.15 g of diethyl bis(2-hydroxyethyl) phosphate into 30 mL of acetone solvent, disperse them evenly, then add 0.04 g of catalyst triethylamine dropwise, react at 10 °C for 5 h, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0025] (3) Add 0.5 g of hydroxyethyl diethyl phosphate modified graphene and 0.1 g of acrylic acid into 20 mL of ethyl acetate, add dropwise 0.008 g of catalyst 4-dimethylaminopyridine and 0.18 g of condensation agent dicyclohexylcarbodiimide, react at 20 °C for 6 h, filter after the reaction, wash with ethyl acetate and acetone to obtain acryloxy diethyl phosphate modified graphene.

[0026] (4) Add 0.75 g of acryloxy diethyl phosphate modified graphene, 5 g of styrene and 0.006 g of polyvinyl alcohol to 50 mL of deionized water and stir evenly. Then, add 0.075 g of dibenzoyl peroxide dropwise and heat to 75 °C for polymerization for 2 h. After the reaction, filter and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0027] (5) 0.2 g of reactive graphene grafted polystyrene, 10 g of impact polystyrene, 0.3 g of plasticizer dioctyl phthalate, and 0.03 g of lubricant ethylene bisstearamide were uniformly blended in a high-speed mixer, and then the mixture was melted and extruded in a twin-screw extruder at 180 °C to obtain reactive graphene flame retardant modified polystyrene plastic. Example 2

[0028] (1) Add 0.2 g of graphene oxide to 15 mL of thionyl chloride, heat to 55 °C and treat for 24 h to obtain graphene chloride.

[0029] (2) Add 0.5 g of acyl chloride graphene and 0.25 g of diethyl bis(2-hydroxyethyl) phosphate into 40 mL of acetone solvent, disperse them evenly, then add 0.08 g of catalyst triethylamine dropwise, react at 20 °C for 20 h, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0030] (3) Add 0.5 g of hydroxyethyl diethyl phosphate modified graphene and 0.2 g of methacrylic acid into 20-80 mL of ethyl acetate, add dropwise 0.015 g of catalyst 4-dimethylaminopyridine and 0.35 g of condensation agent dicyclohexylcarbodiimide, react at 40 °C for 18 h, filter after the reaction, wash with ethyl acetate and acetone to obtain acryloxy diethyl phosphate modified graphene.

[0031] (4) Add 1.2 g of acryloxy diethyl phosphate modified graphene, 5 g of styrene and 0.006-0.009 g of polyvinyl alcohol to 100 mL of deionized water and stir evenly, then drop 0.075-0.125 g of dibenzoyl peroxide and heat to 75-90 °C for polymerization for 2-6 h. After the reaction, filter and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0032] (5) 0.2-1 g of reactive graphene grafted polystyrene, 10 g of impact polystyrene, 0.6 g of plasticizer dioctyl phthalate, and 0.03-0.08 g of lubricant ethylene bisstearamide are uniformly blended in a high-speed mixer, and then the mixture is melted and extruded in a twin-screw extruder at 180-210 °C to obtain reactive graphene flame retardant modified polystyrene plastic. Example 3

[0033] (1) Add 0.2 g of graphene oxide to 15 mL of thionyl chloride, heat to 55-70 °C and treat for 18 h to obtain graphene chloride.

[0034] (2) Add 0.5 g of acyl chloride graphene and 0.45 g of diethyl bis(2-hydroxyethyl) phosphate into 60 mL of acetone solvent, disperse them evenly, then add 0.12 g of catalyst triethylamine dropwise, react at 20 °C for 15 h, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0035] (3) Add 0.5 g of hydroxyethyl diethyl phosphate modified graphene and 0.1-0.4 g of acrylic acid into 60 mL of ethyl acetate, add dropwise 0.022 g of catalyst 4-dimethylaminopyridine and 0.6 g of condensation agent dicyclohexylcarbodiimide, react at 40 °C for 18 h, filter after the reaction, wash with ethyl acetate and acetone to obtain acryloxy diethyl phosphate modified graphene.

[0036] (4) Add 1.6 g of acryloxy diethyl phosphate modified graphene, 5 g of styrene and 0.008 g of polyvinyl alcohol to 50-150 mL of deionized water and stir evenly, then add 0.011 g of dibenzoyl peroxide dropwise and heat to 80 °C to allow polymerization to proceed for 4 h. After the reaction, filter and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0037] (5) 0.8 g of reactive graphene grafted polystyrene, 10 g of impact polystyrene, 0.8 g of plasticizer dioctyl phthalate, and 0.06 g of lubricant ethylene bisstearamide were uniformly blended in a high-speed mixer, and then the mixture was melted and extruded in a twin-screw extruder at 200 °C to obtain reactive graphene flame retardant modified polystyrene plastic. Example 4

[0038] (1) Add 0.2 g of graphene oxide into 20 mL of thionyl chloride, heat to 70 °C and treat for 24 h to obtain graphene chloride.

[0039] (2) Add 0.5 g of acyl chloride graphene and 0.6 g of diethyl bis(2-hydroxyethyl) phosphate into 80 mL of acetone solvent, disperse them evenly, then add 0.15 g of catalyst triethylamine dropwise, react at 30 °C for 20 h, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0040] (3) Add 0.5 g of hydroxyethyl diethyl phosphate modified graphene and 0.4 g of methacrylic acid into 80 mL of ethyl acetate, add dropwise 0.03 g of catalyst 4-dimethylaminopyridine and 0.75 g of condensation agent dicyclohexylcarbodiimide, react at 50 °C for 24 h, filter after the reaction, wash with ethyl acetate and acetone to obtain acryloxy diethyl phosphate modified graphene.

[0041] (4) Add 2 g of acryloxy diethyl phosphate modified graphene, 5 g of styrene and 0.009 g of polyvinyl alcohol to 150 mL of deionized water and stir evenly. Then, add 0.125 g of dibenzoyl peroxide dropwise and heat to 90 °C for polymerization for 6 h. After the reaction, filter and wash with deionized water to obtain reactive graphene grafted polystyrene.

[0042] (5) 1 g of reactive graphene grafted polystyrene, 10 g of impact polystyrene, 1 g of plasticizer dioctyl phthalate, and 0.08 g of lubricant ethylene bisstearamide were uniformly blended in a high-speed mixer, and then the mixture was melted and extruded in a twin-screw extruder at 210 °C to obtain reactive graphene flame retardant modified polystyrene plastic.

[0043] Comparative Example 1 (1) Add 0.2 g of graphene oxide into 20 mL of thionyl chloride, heat to 55 °C and treat for 12 h to obtain graphene chloride.

[0044] (2) Add 0.2 g of acyl chloride graphene and 0.2 g of diethyl bis(2-hydroxyethyl) phosphate into 50 mL of acetone solvent, disperse them evenly, then add 0.08 g of catalyst triethylamine dropwise, react at 10 °C for 20 h, filter and wash with acetone after the reaction to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene.

[0045] (3) 0.4 g of hydroxyethyl diethyl phosphate modified graphene, 10 g of high-impact polystyrene, 0.5 g of plasticizer dioctyl phthalate, and 0.05 g of lubricant ethylene bisstearamide were uniformly blended in a high-speed mixer, and then the mixture was melted and extruded in a twin-screw extruder at 180 °C to obtain graphene-modified polystyrene plastic.

[0046] Comparative Example 2 (1) Add 0.2 g of graphene oxide into 20 mL of thionyl chloride, heat to 70 °C and treat for 12 h to obtain graphene chloride.

[0047] (2) 0.5 g of chlorinated graphene, 10 g of high-impact polystyrene, 0.5 g of plasticizer dioctyl phthalate, and 0.03 g of lubricant ethylene bisstearamide were uniformly blended in a high-speed mixer, and then the mixture was melted and extruded in a twin-screw extruder at 180-210 °C to obtain graphene-modified polystyrene plastic.

[0048] The reactive graphene flame retardant modified polystyrene plastic was made into a film sample with a size of 1 cm×1 cm, and the combustion performance was tested in an MCC microcalorimeter. The test temperature was 20-800 ℃, and the heating rate was 10 ℃ / min.

Claims

1. A method for preparing reactive graphene flame retardant modified polystyrene plastic, characterized in that: The preparation method is as follows: (1) Adding graphene oxide to thionyl chloride, heating to 55-70 °C and treating for 12-24 h to obtain acylated graphene chloride; (2) Adding acyl chloride graphene and diethyl bis(2-hydroxyethyl) phosphate to acetone solvent, dispersing them evenly, and then dropping catalyst triethylamine, reacting at 10-30 °C for 5-20 h to obtain diethyl bis(2-hydroxyethyl) phosphate modified graphene; (3) adding hydroxyethyl diethyl phosphate modified graphene, acrylic acid or methacrylic acid to ethyl acetate, dropping a catalyst 4-dimethylaminopyridine and a condensation agent dicyclohexylcarbodiimide to react, and obtaining acryloxy diethyl phosphate modified graphene; (4) adding 15-40 parts by weight of acryloxy diethyl phosphate modified graphene, 100 parts of styrene and 0.12-0.18 parts of polyvinyl alcohol to deionized water, stirring evenly, then dropping 1.5-2.5 parts of dibenzoyl peroxide, raising the temperature to cause a polymerization reaction, and obtaining reactive graphene grafted polystyrene; (5) Reactive graphene grafted polystyrene, high impact polystyrene, plasticizer dioctyl phthalate, and lubricant ethylene bisstearamide are uniformly blended in a high-speed mixer, and then the mixture is melted and extruded in a twin-screw extruder at 180-210 °C to obtain reactive graphene flame retardant modified polystyrene plastic.

2. The method for preparing a reactive graphene flame retardant modified polystyrene plastic according to claim 1, characterized in that: In the step (2), the acyl chloride graphene is 100 parts, the diethyl bis(2-hydroxyethyl)phosphate is 30-120 parts, and the triethylamine is 8-30 parts, by weight.

3. The method for preparing a reactive graphene flame retardant modified polystyrene plastic according to claim 1, characterized in that: In the step (3), the reaction is carried out at 20-50°C for 6-24 hours.

4. The method for preparing a reactive graphene flame retardant modified polystyrene plastic according to claim 1, characterized in that: In the step (3), the graphene modified with diethyl hydroxyethyl phosphate is 100 parts, acrylic acid or methacrylic acid is 18-80 parts, 4-dimethylaminopyridine is 1.5-6 parts, and the condensation agent dicyclohexylcarbodiimide is 35-150 parts by weight.

5. The method for preparing a reactive graphene flame retardant modified polystyrene plastic according to claim 1, characterized in that: The reaction in step (4) is carried out at 75-90°C for 2-6 hours.

6. The method for preparing a reactive graphene flame retardant modified polystyrene plastic according to claim 1, characterized in that: In the step (5), the reactive graphene grafted polystyrene is 2-10 parts and the high impact polystyrene is 100 parts by weight.

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