Phosphorus-containing flame retardant with epoxy group as well as preparation method and application of flame retardant

Abstract

The invention provides a phosphorus-containing flame retardant with an epoxy group as well as a preparation method and application of the flame retardant. The phosphorus-containing flame retardant with the epoxy group has a structure as shown in a formula I. The phosphorus-containing flame retardant with the epoxy group, provided by the invention, can be used as an active diluent of an epoxy coating, and not only has the effect of reducing the viscosity, but also has the effect of flame retardance. Compared with additive flame retardants, as the phosphorus-containing flame retardant with the epoxy group is fixed in a molecular chain of epoxy resin after the epoxy coating is cured, the flame retardant cannot be separated out due to migration of small molecules or dissolution in water, so that the obtained epoxy coating has relatively high adhesive force stability and flame retardant stability, and environmental protection, safety and no harm can be truly achieved.

Description

technical field

[0001] The invention belongs to the technical field of flame retardants, and relates to a phosphorus-containing flame retardant with an epoxy group and a preparation method and application thereof. Background technique

[0002] Epoxy resin is a general term for a class of polymers containing more than two epoxy groups in the molecule. Due to the high chemical activity of the epoxy group, a variety of compounds containing active hydrogen can be used to open the ring, cure and cross-link to form a network structure, so it is a thermosetting resin. Epoxy resins are widely used in many fields such as adhesives, potting adhesives, self-leveling floors, and copper clad laminates.

[0003] Epoxy coatings are easy to cure, strong adhesion, low shrinkage after curing, and have good mechanical and electrical properties. Antirust primer for platforms, harbor facilities, automobile chassis surfaces, and outer walls of oil tanks.

[0004] As a polymer material, epoxy r...

Examples

preparation example 1

[0069] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0070]

[0071] The preparation method is as follows:

[0072] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of methacrylic acid into a three-port 200mL glass reactor with a stirring device, and dissolve 1mmol of Pb catalyst in 20mL of glacial acetic acid, then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until neutral, dried After obtaining intermediate 1;

[0073](2) Add the intermediate 1 obtained in step 1, 2 mol of epichlorohydrin and 0.02 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 100 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the mixture at 110° C. Sti...

preparation example 2

[0076] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0077]

[0078] The preparation method is as follows:

[0079] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of acrylic acid into a three-port 200mL glass reactor with a stirring device, and dissolve 1mmol of Pb catalyst in 20mL of ice at 60°C under stirring conditions. Acetic acid, then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until neutral, dried to obtain Intermediate 1;

[0080] (2) Add the intermediate 1 obtained in step 1, 2 mol of epichlorohydrin and 0.02 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 100 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the m...

preparation example 3

[0083] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0084]

[0085] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of tetrahydrophthalic anhydride into a three-port 200mL glass reactor with a stirring device, and mix 1mmol of The Pb catalyst was dissolved in 20mL of glacial acetic acid, and then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until Neutral, intermediate 1 is obtained after drying;

[0086] (2) Add the intermediate 1 obtained in step 1, 3 mol of epichlorohydrin and 0.04 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 150 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the mixture at 110° C. Stir and react for...

technical field

[0001] The invention belongs to the technical field of flame retardants, and relates to a phosphorus-containing flame retardant with an epoxy group and a preparation method and application thereof. Background technique

[0002] Epoxy resin is a general term for a class of polymers containing more than two epoxy groups in the molecule. Due to the high chemical activity of the epoxy group, a variety of compounds containing active hydrogen can be used to open the ring, cure and cross-link to form a network structure, so it is a thermosetting resin. Epoxy resins are widely used in many fields such as adhesives, potting adhesives, self-leveling floors, and copper clad laminates.

[0003] Epoxy coatings are easy to cure, strong adhesion, low shrinkage after curing, and have good mechanical and electrical properties. Antirust primer for platforms, harbor facilities, automobile chassis surfaces, and outer walls of oil tanks.

[0004] As a polymer material, epoxy r...

Examples

preparation example 1

[0069] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0070]

[0071] The preparation method is as follows:

[0072] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of methacrylic acid into a three-port 200mL glass reactor with a stirring device, and dissolve 1mmol of Pb catalyst in 20mL of glacial acetic acid, then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until neutral, dried After obtaining intermediate 1;

[0073](2) Add the intermediate 1 obtained in step 1, 2 mol of epichlorohydrin and 0.02 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 100 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the mixture at 110° C. Sti...

preparation example 2

[0076] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0077]

[0078] The preparation method is as follows:

[0079] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of acrylic acid into a three-port 200mL glass reactor with a stirring device, and dissolve 1mmol of Pb catalyst in 20mL of ice at 60°C under stirring conditions. Acetic acid, then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until neutral, dried to obtain Intermediate 1;

[0080] (2) Add the intermediate 1 obtained in step 1, 2 mol of epichlorohydrin and 0.02 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 100 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the m...

preparation example 3

[0083] A phosphorus-containing flame retardant with an epoxy group, the structure is as follows:

[0084]

[0085] (1) Under a nitrogen atmosphere, put 50mL of glacial acetic acid, 1mol of dimethyl phosphite and 1mol of tetrahydrophthalic anhydride into a three-port 200mL glass reactor with a stirring device, and mix 1mmol of The Pb catalyst was dissolved in 20mL of glacial acetic acid, and then added dropwise to the above reaction system, reacted at 60°C for 12h, then added saturated sodium carbonate solution, separated the water phase with a separatory funnel, dehydrated under reduced pressure and washed with water until Neutral, intermediate 1 is obtained after drying;

[0086] (2) Add the intermediate 1 obtained in step 1, 3 mol of epichlorohydrin and 0.04 mol of triethylbenzyl ammonium chloride into a 1000 mL three-necked glass flask, and simultaneously add 150 mL of 40 wt % sodium hydroxide aqueous solution dropwise, and heat the mixture at 110° C. Stir and react for...

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