Phosphorus-nitrogen nano flame retardant of core-shell structure and preparation method thereof

Abstract

The invention relates to a nano flame retardant epoxy resin composite material and a preparation method thereof and belongs to the technical field of flame retardants. A one-step method is adopted, the surface of a carbon nano tube is coated with a novel phosphorus-nitrogen flame retardant obtained through polycondensation on phenylphosphonic dichloride and 4,4'-diaminodiphenylmethane under Phi-Phi stacking interaction, and the composite material of the core-shell structure is formed. The preparation method provided by the invention has the advantages that structure and properties of the carbon nano tube can not be damaged, reaction conditions are mild, requirements on equipment are low, less waste is produced, and the prepared composite material can be taken as a novel polymeric flame retardant.

Description

technical field

[0001] The invention relates to a preparation method of a phosphorus-nitrogen series nano-flame retardant with a core-shell structure, belongs to the preparation of a novel high-efficiency halogen-free flame-retardant material by a chemical synthesis method, and belongs to the technical field of flame retardants. Background technique

[0002] Since the discovery of carbon nanotubes in 1991, its unique structure combined with its excellent mechanical, electrical and chemical properties has attracted widespread attention in many fields such as chemistry, physics and material science.

[0003] The use of carbon nanotubes to improve the flame retardancy of polymers was first proposed by Beyer in 2002. Since then, people have made many attempts to use carbon nanotubes in polymer flame retardancy, but carbon nanotubes are used alone as polymers. The flame retardant efficiency of the material's flame retardant is not high, and it is difficult to pass the traditional...

Examples

Embodiment 1

[0026] Add 1.00g of carbon nanotubes and 3.09g of triethylamine into a three-necked flask containing 200mL of xylene, pre-disperse for 120min under the action of 200W ultrasonic waves; add 2.48g of phenylphosphonic acid dichloride, stir evenly, and maintain the reaction system At a temperature of 0°C, add 3.02g of 4,4'-diaminodiphenylmethane in 50mL of xylene solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 60°C for 12 hours; filter the reaction mixture with suction, and then use two Wash 3 times with toluene, and then wash 3 times with deionized water, and dry the obtained solid product under vacuum at 80°C to constant weight to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant with a yield of 90.4%. The layer quality fraction is 77.1%.

Embodiment 2

[0028] Add 1.00g of carbon nanotubes and 6.18g of triethylamine into a three-necked flask containing 240mL of tetrahydrofuran, and pre-disperse for 90 minutes under the action of 250W ultrasound; add 4.96g of phenylphosphonic acid dichloride, stir well, and maintain the temperature of the reaction system to 5°C, add 6.05g of 4,4'-diaminodiphenylmethane in 60mL tetrahydrofuran solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 50°C for 10 hours; filter the reaction mixture with suction, and then wash it with tetrahydrofuran for 3 times, and then washed 4 times with deionized water, and the resulting solid product was dried to constant weight under vacuum at 70°C to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant, with a yield of 85.7%, and the shell mass fraction was 80.8%.

Embodiment 3

[0030] Add 1.00g of carbon nanotubes and 12.95g of sodium carbonate into a three-necked flask filled with 300mL of acetone, and pre-disperse for 60 minutes under the action of 300W ultrasound; -5°C, add 12.10g of 4,4'-diaminodiphenylmethane in 70mL of acetone solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 45°C for 14 hours; filter the reaction mixture with suction, and then wash it with acetone for 3 times, and then washed 3 times with deionized water, and the resulting solid product was dried to constant weight under vacuum at 75°C to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant with a yield of 86.2%, and the shell mass fraction was 92.7%.

technical field

[0001] The invention relates to a preparation method of a phosphorus-nitrogen series nano-flame retardant with a core-shell structure, belongs to the preparation of a novel high-efficiency halogen-free flame-retardant material by a chemical synthesis method, and belongs to the technical field of flame retardants. Background technique

[0002] Since the discovery of carbon nanotubes in 1991, its unique structure combined with its excellent mechanical, electrical and chemical properties has attracted widespread attention in many fields such as chemistry, physics and material science.

[0003] The use of carbon nanotubes to improve the flame retardancy of polymers was first proposed by Beyer in 2002. Since then, people have made many attempts to use carbon nanotubes in polymer flame retardancy, but carbon nanotubes are used alone as polymers. The flame retardant efficiency of the material's flame retardant is not high, and it is difficult to pass the traditional...

Examples

Embodiment 1

[0026] Add 1.00g of carbon nanotubes and 3.09g of triethylamine into a three-necked flask containing 200mL of xylene, pre-disperse for 120min under the action of 200W ultrasonic waves; add 2.48g of phenylphosphonic acid dichloride, stir evenly, and maintain the reaction system At a temperature of 0°C, add 3.02g of 4,4'-diaminodiphenylmethane in 50mL of xylene solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 60°C for 12 hours; filter the reaction mixture with suction, and then use two Wash 3 times with toluene, and then wash 3 times with deionized water, and dry the obtained solid product under vacuum at 80°C to constant weight to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant with a yield of 90.4%. The layer quality fraction is 77.1%.

Embodiment 2

[0028] Add 1.00g of carbon nanotubes and 6.18g of triethylamine into a three-necked flask containing 240mL of tetrahydrofuran, and pre-disperse for 90 minutes under the action of 250W ultrasound; add 4.96g of phenylphosphonic acid dichloride, stir well, and maintain the temperature of the reaction system to 5°C, add 6.05g of 4,4'-diaminodiphenylmethane in 60mL tetrahydrofuran solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 50°C for 10 hours; filter the reaction mixture with suction, and then wash it with tetrahydrofuran for 3 times, and then washed 4 times with deionized water, and the resulting solid product was dried to constant weight under vacuum at 70°C to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant, with a yield of 85.7%, and the shell mass fraction was 80.8%.

Embodiment 3

[0030] Add 1.00g of carbon nanotubes and 12.95g of sodium carbonate into a three-necked flask filled with 300mL of acetone, and pre-disperse for 60 minutes under the action of 300W ultrasound; -5°C, add 12.10g of 4,4'-diaminodiphenylmethane in 70mL of acetone solution dropwise. After the dropwise addition, raise the temperature of the reaction system to 45°C for 14 hours; filter the reaction mixture with suction, and then wash it with acetone for 3 times, and then washed 3 times with deionized water, and the resulting solid product was dried to constant weight under vacuum at 75°C to obtain a core-shell structure phosphorus-nitrogen nano-flame retardant with a yield of 86.2%, and the shell mass fraction was 92.7%.

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