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Research on organophosphorus flame retardants
2017-9-8 16:43:43
Research on organophosphorus flame retardants
This paper describes the recent progress in the research of organophosphorus flame retardants in China and abroad, and introduces the properties, characteristics and application of organophosphorus flame retardants.
In recent decades, fire caused by macromolecule material has caused a great threat to people's life and safety, thus the flame retardant treatment of building materials has attracted much attention. There are several kinds of flame retardants, including organic halide, organophosphorus and inorganic flame retardant. Phosphorus-containing flame retardant since the 1960 s is the runway in the field of flame retardant, the reason is that not only this kind of fire retardants of high efficiency, less consumption, small influence on the performance of the material, and the price is moderate.
But since 1986, phosphorus-containing flame retardant suffer the dioxins problem, coupled with its flame retardant polymer materials in the hot crack and combustion generated when a lot of smoke and corrosive gas, the application of phosphorus-containing flame retardants is not optimistic. In countries such as Europe and the United States, more and more users, especially the electronics and electric industry, are cautious about halogen flame retardants.
Inorganic flame retardants have emerged in recent years, with the advantages of low toxicity, low smoke, low corrosion and low price. However, due to the large amount of added quantity, the mechanical properties of the material can be affected, which limits its application. Organophosphorus flame retardant is not a new flame retardant, but its low smoke, low toxicity, halogen-free and other advantages, in the environmental protection requirements of higher and higher today, gradually attracted people's favor. The study of organophosphorus flame retardant is increasing.
Early development and application of organic phosphorus flame retardants are: triphenyl phosphate and phosphoric acid ester (xylene), triethyl phosphate and phosphoric acid isopropyl benzene ester, three trioctyl phosphate, methyl phenyl diphenyl phosphonic acid ester, three (beta - ethyl chloride) phosphate ester, phosphate (2, 3 - two br propyl) ester, three (two br phenyl) phosphate ester, etc.
Tris (2-Chloroethyl) Phosphate
There Are Three Industrial Methods: Phosphorus Oxychloride And Chloroethanol Reaction; Phosphorus Trichloride And Chloroethanol Reaction Reoxidation; Phosphorus Oxychloride And Ethylene Oxide Reaction (Industrial Commonly Used Method).
1, Phosphorus Oxychloride And Ethylene Oxide To Sodium Metavanadate As A Catalyst, At 50 ° C Reaction, The Reaction By Neutralization, Washing, Vacuum Dehydration Off The Low Boiling, That Is, The Finished Product. Chlorohydrin Can Also Be Used As Raw Materials, And Phosphorus Oxychloride Or Phosphorus Trichloride Reaction To Produce Tris (2-Chloro Ethyl) Phosphate.
2, 326 Kg Of Phosphorus Oxychloride And 1.0 Kg Of Sodium Metavanadate Into The Reactor. The Nitrogen In The Autoclave Was Driven By Nitrogen, And 650 Kg Of Ethylene Oxide Was Introduced Under Vacuum And Stirred At 45 To 50 ° C For 2 To 3 Hours. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated. Finished Product.
3. Put Phosphorus Oxychloride And Sodium Metaphosphate Into The Reactor. Nitrogen To Drive The Air, In The Vacuum Under The Access To Ethylene Oxide, At 45 ~ 50 ℃ Stirring 2 ~ 3h. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated Finished.
Tris (2-Chloroethyl) Phosphate use
1. Tris (2-Chloroethyl) Phosphate Has Excellent Flame Retardancy, Excellent Resistance To Low Temperature And UV Resistance, The Steam Can Only Be Used At 225 ℃ Above The Direct Ignition Can Be Fired, But The Fire The Source Is Immediately Self-Extinguishing. This Product Is A Flame Retardant Not Only Can Improve The Material Level Of Flame Retardant Materials, But Also Improve The Flame Resistance Of Water Resistance, Acid Resistance, Cold Resistance And Antistatic Properties. Commonly Used In Flame Retardant Nitrocellulose And Acetate Fiber As The Substrate Of Paint Coatings, Unsaturated Polyester, Polyurethane, Acrylic, Phenolic Resin, Can Also Be Used For Soft PVC Plastic Flame Retardant. This Product Is Used For The Amount Of Unsaturated Polyester 10% To 20%, In The Polyurethane Rigid Foam (Flame Retardant Polyether As Raw Material) Can Be About 10% In The Soft PVC Used As Auxiliary Plastic Flame Retardant When The 5% To 10%. Flame Retardants, Uranium, Thorium, Plutonium, Technetium And Other Rare Metal Separation Solvent Or Extractant.
2. This Product Is Widely Used In Chemical Fiber Fabrics, Cellulose Acetate As A Flame Retardant, In Addition To Self-Extinguishing, But Also Improve Water Resistance, Cold Resistance And Antistatic Properties. The General Amount Of 5 To 10 Copies. This Product Is An Excellent Flame Retardant For Synthetic Materials, And Has A Good Role In The Promotion, Widely Used In Cellulose Acetate, Nitrocellulose Varnish, Ethyl Cellulose, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane, Phenolic Resin , In Addition To Self-Extinguishing Products, But Also Improve The Physical Properties Of Products, Products Feel Soft, Also Known As Oil Additives And Rare Elements Of The Extractant, And Flame Retardant Rubber Conveyor Belt Is The Main Flame Retardant Materials , The General Amount Of Added 5% To 10%.
3. Used As Additive Type Halogenated Phosphate Flame Retardant And Plasticizer. Molecules In Both Phosphorus And Chlorine, Flame Retardant Effect Is Remarkable, Not Volatile And Hydrolysis, Good Stability To Ultraviolet Light. Applicable To Phenolic Resin, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane And So On. Also Used As Nitrocellulose Coating Flame Retardant, PVC Flame Retardant Plasticizer, Metal Extractant, Gasoline Additives And Polyimide Processing Aids And So On. Can Improve Water Resistance, Weatherability, Cold Resistance, Antistatic Property. Reference Dosage 5% To 20%.
But these phosphate products are mostly liquid, poor heat resistance and high volatility, which affect the flame retardant effect and flame retardant durability. Phosphorous halogen flame retardant is also due to its halogen and other problems, the application is limited. Therefore, the research and development of new environment-friendly organophosphorus flame retardants, which are of low volatility, good heat resistance and lasting flame retardation, have become a hot topic in the present study.
For the industrialization of organic phosphorus flame retardants volatile big, poor thermal stability and toxicity of phosphorus halogen flame retardant, reported at home and abroad in recent years a large number of new organic phosphorus flame retardants, and the part has been industrialized. The high efficiency, low smoke, low toxicity, green environmental protection and other advantages of the flame retardant with nitrogen and silicon as flame retardant are widely concerned. In the molecular design of organophosphorus flame retardant, phosphorus-nitrogen flame retardants or phospho-silicon flame retardants, which are introduced in nitrogen or silicon elements, can often play a synergistic flame retardant effect.
Bisphenol A double (diphenyl phosphate) (BDP) and polyphenol biphenol (diphenyl phosphate) (RDP) are the new non-halogen organophosphorous flame retardants developed in recent years. Compared with traditional organophosphorous flame retardants, they have high molecular weight, high thermal stability, low volatility and high flame retardant efficiency. As the additive flame retardant of high polymer, it is mainly used in thermoplastic engineering plastics such as PC/ABS blend, polyethylene and foam polyurethane, showing excellent flame retardant effect. At present, the two kinds of flame retardants have been produced and sold by many companies in China and abroad.
In 2000, li xin et al synthesized a new type of highly symmetrical pannular phosphate Trimer. The compound high phosphorus content, good thermal stability, the initial decomposition temperature is 316 ℃, can satisfy the requirement of the engineering plastics processing. When it is mixed with polyphosphate and melamine, it is better than the industrial flame retardant PEPA.
2004 Noriaki reported the following structure such as amount of high phosphorus containing flame retardants, they do not contain halogen, low volatility, good thermal stability, used in polyurethane foam, polyester and other materials, flame retardant effect is a plus.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
This paper describes the recent progress in the research of organophosphorus flame retardants in China and abroad, and introduces the properties, characteristics and application of organophosphorus flame retardants.
In recent decades, fire caused by macromolecule material has caused a great threat to people's life and safety, thus the flame retardant treatment of building materials has attracted much attention. There are several kinds of flame retardants, including organic halide, organophosphorus and inorganic flame retardant. Phosphorus-containing flame retardant since the 1960 s is the runway in the field of flame retardant, the reason is that not only this kind of fire retardants of high efficiency, less consumption, small influence on the performance of the material, and the price is moderate.
But since 1986, phosphorus-containing flame retardant suffer the dioxins problem, coupled with its flame retardant polymer materials in the hot crack and combustion generated when a lot of smoke and corrosive gas, the application of phosphorus-containing flame retardants is not optimistic. In countries such as Europe and the United States, more and more users, especially the electronics and electric industry, are cautious about halogen flame retardants.
Inorganic flame retardants have emerged in recent years, with the advantages of low toxicity, low smoke, low corrosion and low price. However, due to the large amount of added quantity, the mechanical properties of the material can be affected, which limits its application. Organophosphorus flame retardant is not a new flame retardant, but its low smoke, low toxicity, halogen-free and other advantages, in the environmental protection requirements of higher and higher today, gradually attracted people's favor. The study of organophosphorus flame retardant is increasing.
Early development and application of organic phosphorus flame retardants are: triphenyl phosphate and phosphoric acid ester (xylene), triethyl phosphate and phosphoric acid isopropyl benzene ester, three trioctyl phosphate, methyl phenyl diphenyl phosphonic acid ester, three (beta - ethyl chloride) phosphate ester, phosphate (2, 3 - two br propyl) ester, three (two br phenyl) phosphate ester, etc.
Tris (2-Chloroethyl) Phosphate
There Are Three Industrial Methods: Phosphorus Oxychloride And Chloroethanol Reaction; Phosphorus Trichloride And Chloroethanol Reaction Reoxidation; Phosphorus Oxychloride And Ethylene Oxide Reaction (Industrial Commonly Used Method).
1, Phosphorus Oxychloride And Ethylene Oxide To Sodium Metavanadate As A Catalyst, At 50 ° C Reaction, The Reaction By Neutralization, Washing, Vacuum Dehydration Off The Low Boiling, That Is, The Finished Product. Chlorohydrin Can Also Be Used As Raw Materials, And Phosphorus Oxychloride Or Phosphorus Trichloride Reaction To Produce Tris (2-Chloro Ethyl) Phosphate.
2, 326 Kg Of Phosphorus Oxychloride And 1.0 Kg Of Sodium Metavanadate Into The Reactor. The Nitrogen In The Autoclave Was Driven By Nitrogen, And 650 Kg Of Ethylene Oxide Was Introduced Under Vacuum And Stirred At 45 To 50 ° C For 2 To 3 Hours. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated. Finished Product.
3. Put Phosphorus Oxychloride And Sodium Metaphosphate Into The Reactor. Nitrogen To Drive The Air, In The Vacuum Under The Access To Ethylene Oxide, At 45 ~ 50 ℃ Stirring 2 ~ 3h. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated Finished.
Tris (2-Chloroethyl) Phosphate use
1. Tris (2-Chloroethyl) Phosphate Has Excellent Flame Retardancy, Excellent Resistance To Low Temperature And UV Resistance, The Steam Can Only Be Used At 225 ℃ Above The Direct Ignition Can Be Fired, But The Fire The Source Is Immediately Self-Extinguishing. This Product Is A Flame Retardant Not Only Can Improve The Material Level Of Flame Retardant Materials, But Also Improve The Flame Resistance Of Water Resistance, Acid Resistance, Cold Resistance And Antistatic Properties. Commonly Used In Flame Retardant Nitrocellulose And Acetate Fiber As The Substrate Of Paint Coatings, Unsaturated Polyester, Polyurethane, Acrylic, Phenolic Resin, Can Also Be Used For Soft PVC Plastic Flame Retardant. This Product Is Used For The Amount Of Unsaturated Polyester 10% To 20%, In The Polyurethane Rigid Foam (Flame Retardant Polyether As Raw Material) Can Be About 10% In The Soft PVC Used As Auxiliary Plastic Flame Retardant When The 5% To 10%. Flame Retardants, Uranium, Thorium, Plutonium, Technetium And Other Rare Metal Separation Solvent Or Extractant.
2. This Product Is Widely Used In Chemical Fiber Fabrics, Cellulose Acetate As A Flame Retardant, In Addition To Self-Extinguishing, But Also Improve Water Resistance, Cold Resistance And Antistatic Properties. The General Amount Of 5 To 10 Copies. This Product Is An Excellent Flame Retardant For Synthetic Materials, And Has A Good Role In The Promotion, Widely Used In Cellulose Acetate, Nitrocellulose Varnish, Ethyl Cellulose, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane, Phenolic Resin , In Addition To Self-Extinguishing Products, But Also Improve The Physical Properties Of Products, Products Feel Soft, Also Known As Oil Additives And Rare Elements Of The Extractant, And Flame Retardant Rubber Conveyor Belt Is The Main Flame Retardant Materials , The General Amount Of Added 5% To 10%.
3. Used As Additive Type Halogenated Phosphate Flame Retardant And Plasticizer. Molecules In Both Phosphorus And Chlorine, Flame Retardant Effect Is Remarkable, Not Volatile And Hydrolysis, Good Stability To Ultraviolet Light. Applicable To Phenolic Resin, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane And So On. Also Used As Nitrocellulose Coating Flame Retardant, PVC Flame Retardant Plasticizer, Metal Extractant, Gasoline Additives And Polyimide Processing Aids And So On. Can Improve Water Resistance, Weatherability, Cold Resistance, Antistatic Property. Reference Dosage 5% To 20%.
But these phosphate products are mostly liquid, poor heat resistance and high volatility, which affect the flame retardant effect and flame retardant durability. Phosphorous halogen flame retardant is also due to its halogen and other problems, the application is limited. Therefore, the research and development of new environment-friendly organophosphorus flame retardants, which are of low volatility, good heat resistance and lasting flame retardation, have become a hot topic in the present study.
For the industrialization of organic phosphorus flame retardants volatile big, poor thermal stability and toxicity of phosphorus halogen flame retardant, reported at home and abroad in recent years a large number of new organic phosphorus flame retardants, and the part has been industrialized. The high efficiency, low smoke, low toxicity, green environmental protection and other advantages of the flame retardant with nitrogen and silicon as flame retardant are widely concerned. In the molecular design of organophosphorus flame retardant, phosphorus-nitrogen flame retardants or phospho-silicon flame retardants, which are introduced in nitrogen or silicon elements, can often play a synergistic flame retardant effect.
Bisphenol A double (diphenyl phosphate) (BDP) and polyphenol biphenol (diphenyl phosphate) (RDP) are the new non-halogen organophosphorous flame retardants developed in recent years. Compared with traditional organophosphorous flame retardants, they have high molecular weight, high thermal stability, low volatility and high flame retardant efficiency. As the additive flame retardant of high polymer, it is mainly used in thermoplastic engineering plastics such as PC/ABS blend, polyethylene and foam polyurethane, showing excellent flame retardant effect. At present, the two kinds of flame retardants have been produced and sold by many companies in China and abroad.
In 2000, li xin et al synthesized a new type of highly symmetrical pannular phosphate Trimer. The compound high phosphorus content, good thermal stability, the initial decomposition temperature is 316 ℃, can satisfy the requirement of the engineering plastics processing. When it is mixed with polyphosphate and melamine, it is better than the industrial flame retardant PEPA.
2004 Noriaki reported the following structure such as amount of high phosphorus containing flame retardants, they do not contain halogen, low volatility, good thermal stability, used in polyurethane foam, polyester and other materials, flame retardant effect is a plus.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
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