News Details
Phosphor containing flame retardant for Polyurethane
2017-12-1 10:50:18
Phosphor containing flame retardant for Polyurethane
Organic flame retardant agent in solid phase and its unique carbon and quality retention mechanism and gas phase mechanism of flame retardant polyurethane, flame retardant in the process can not only reduce the heat release rate, improve the flame retardant effect, but also overcome the halogen flame retardant combustion is easy to emit irritating and corrosive gases and disadvantages of hydrogen halide a lot of poisonous gas, is one of the important development direction of research and development of flame retardant.
In the process of polyurethane containing phoxim flame retardant, found pentaerythritol polyol synthesis of a series of cyclic phosphonate ester has a better flame retardant efficiency than fatty phosphonate, they have abundant carbon source and acid source, play an important role in the intumescent flame retardant agent. A large number of studies have shown that sulfur is also an effective flame retardant element, which has a synergistic effect with phosphorus. The polyurethane flame retardant with phosphor system has been developed greatly.
In this paper, phosphorus trichloride, benzene, sulfur powder, thio phenyl phosphonic chloride was synthesized by the reaction of friede-crafts two (3) (phenylphosphonothioic, dichloride) thio phenyl phosphonic chloride two with pentaerythritol or neopentyl glycol reaction for the synthesis of a novel flame retardant 2,4,8,10- four -3,9- two -3,9- two oxa sulfur phenyl -3,9- two p hetero spiro eleven alkyl ring [5.5]
(1) (1) (2,4,8,10-tetraoxa-3,9-dithio-3,9-diphenyl-3,9-diphosphaspiro[5,5]-undecane) and 5,5- two methyl -2- phenyl -2- thiosulfate two oxyphosphorus heterocyclane
(2) (5,5-dimethyl-2-phenyl-2-thio-1,3,2-dioxaphosphorinane) (scheme 1). In the synthesis of thiophenyl phosphonyl two chlorine, the problem that the catalyst AlCl3 can not be removed from the post-treatment by the ionic liquid method is avoided. The results of thermal properties show that compound 1 has good charcoal properties and is a potential excellent flame retardant.
Bruker av400 MHz nuclear magnetic resonance (DMSO-d6 as solvent, TMS as internal standard); Perkin-Elmer 2000 FT-IR infrared spectrometer (KBr chip); DSC 204 F1 differential thermal scanning calorimeter.
The 209 F1 type thermogravimetric differential thermal analysis thermal analyzer (heating rate is 10.Min-1, the heating range is from room temperature to 600 degrees, high purity nitrogen protection, gas flow rate is 20 ml.min-1), wya Abbe refractometer.
In pyridine and KOH reflux for two hours, distillation, collected from 114 to 116 DEG C and anhydrous dichloromethane fraction; K2CO3 dry weight three [et3nh]cl, triethylamine hydrochloride steaming; phosphorus trichloride, aluminium chloride, sulfur powder is pure.
Tris(2-chloroethyl)phosphate(TCEP)
Appearance: Pure Tris (2-Chloroethyl) Phosphate Is A Colorless Or Pale Yellow Oily Transparent Liquid With A Light Creamy Taste.
Refractive Index (N20D) 1.4731
Boiling Point Of 194 ° C, Flash Point Of 225 ° C
Freezing Point -64 ℃
Decomposition Temperature 240-280 ℃
Viscosity 38-47 Centipoise (20 ° C)
Phosphorus Content Of 10.8%
Chlorine Content Of 37.3%, With The General Organic Solvents (Such As Alcohol, Ketones, Aromatics, Chloroform, Etc.) Compatible, Insoluble In Aliphatic Hydrocarbons, Almost Insoluble In Water, And Hydrolytic Stability Is Good, In Alkaline Solution In A Small Amount Of Decomposition, The No Obvious Corrosion Of The Product.
Tris(2-chloroethyl)phosphate(TCEP)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%.
Synthesis (1) the preparation of ionic liquid [et3nh]cl-2alcl3. In nitrogen atmosphere, 13.8g (0.1mol) three ethylamine hydrochloride was added into the flask, then 26.67g (0.2mol) was added slowly, and the aluminum chloride was stirred up. Then the ionic liquid [et3nh]cl-2alcl3 was added after stirring 3H.
(2) compound thiophenyl phosphonic acid two chlorine (3) synthesis [14] to P C L 3 (34.4 g, 0.25 m o l) and [e t 3N]] after the addition of 6.5 6.5 (benzene) to the reflux solution of "e t 3N"], after adding up, it continues to reflux at 78-80 degrees. The mixture is cold to room temperature, and the 30min is placed. Then the excess PCl3 was evaporated at 40 degrees C.
The residual liquid cooled to 30 DEG C, and then batch addition of 28.4g sulfur powder (0.0887mol), to ensure that the reaction temperature at 80 degrees celsius. After adding 80 centigrade, the reaction was 1.5h. After cooling the reactant, add petroleum ether to stir 30min. After the stirring is stopped, the solution is stratified, the upper layer is petroleum ether phase, and the lower layer is ionic liquid phase.
The petroleum ether is separated and collected, and the unreacted two chlorinated phosphine phosphine is removed with cold water and then dried with anhydrous CaCl2 and decompressed to evaporate petroleum ether. The distillates at 150 degrees centigrade at 1333 PA were collected, with a yield of 52%. The measured density D25 is 1.394 (g/ml), and the refractive index n25d is 1.6180 (literature value: d25=1.390, n25d=1.6178-1.6182).
(3) compound 2,4,8,10- four oxa -3,9- two -3,9- two -3,9- two phenyl sulfide phosphaspirocyclic [5.5] eleven alkanes (1) synthesis of pentaerythritol 1.4g (about 0.01mol) and 3.2ml (0.04mol) dispersed in 30ml pyridine in dichloromethane, the ice water bath and cooled to 0 DEG C, 4.2g (0.02mol) phenyl phosphine sulfide generation two acyl chloride (5ml dissolved in dichloromethane) under stirring drops. Continue the ice bath and stir 15min, and then slowly heat up to 55 C reflux reaction. TLC followed up the reaction process. After 5h, the reaction ended. After spin evaporation, the white powder was removed. The distilled water was washed for three times. The white powder was recrystallized by acetonitrile, and the yield was 1, the yield was 75%.
(4) synthetic compound 2 of compound 5,5- two methyl -2- phenyl -2- thiosulfate two oxo heterocyclane (2) is similar to 1. The yield is 68%.
The reaction of the preparation of 1 and 2 was carried out according to the SN2 process, and the polarity of the solvent was not beneficial to the reaction, so dichloromethane was selected as the solvent. Pyridine, as a compress, can absorb the HCl produced by the reaction very well and promote the positive reaction. Compared with the literature, acetonitrile is selected as the solvent for recrystallization in the post-processing, and the purity of the product is higher.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
Organic flame retardant agent in solid phase and its unique carbon and quality retention mechanism and gas phase mechanism of flame retardant polyurethane, flame retardant in the process can not only reduce the heat release rate, improve the flame retardant effect, but also overcome the halogen flame retardant combustion is easy to emit irritating and corrosive gases and disadvantages of hydrogen halide a lot of poisonous gas, is one of the important development direction of research and development of flame retardant.
In the process of polyurethane containing phoxim flame retardant, found pentaerythritol polyol synthesis of a series of cyclic phosphonate ester has a better flame retardant efficiency than fatty phosphonate, they have abundant carbon source and acid source, play an important role in the intumescent flame retardant agent. A large number of studies have shown that sulfur is also an effective flame retardant element, which has a synergistic effect with phosphorus. The polyurethane flame retardant with phosphor system has been developed greatly.
In this paper, phosphorus trichloride, benzene, sulfur powder, thio phenyl phosphonic chloride was synthesized by the reaction of friede-crafts two (3) (phenylphosphonothioic, dichloride) thio phenyl phosphonic chloride two with pentaerythritol or neopentyl glycol reaction for the synthesis of a novel flame retardant 2,4,8,10- four -3,9- two -3,9- two oxa sulfur phenyl -3,9- two p hetero spiro eleven alkyl ring [5.5]
(1) (1) (2,4,8,10-tetraoxa-3,9-dithio-3,9-diphenyl-3,9-diphosphaspiro[5,5]-undecane) and 5,5- two methyl -2- phenyl -2- thiosulfate two oxyphosphorus heterocyclane
(2) (5,5-dimethyl-2-phenyl-2-thio-1,3,2-dioxaphosphorinane) (scheme 1). In the synthesis of thiophenyl phosphonyl two chlorine, the problem that the catalyst AlCl3 can not be removed from the post-treatment by the ionic liquid method is avoided. The results of thermal properties show that compound 1 has good charcoal properties and is a potential excellent flame retardant.
Bruker av400 MHz nuclear magnetic resonance (DMSO-d6 as solvent, TMS as internal standard); Perkin-Elmer 2000 FT-IR infrared spectrometer (KBr chip); DSC 204 F1 differential thermal scanning calorimeter.
The 209 F1 type thermogravimetric differential thermal analysis thermal analyzer (heating rate is 10.Min-1, the heating range is from room temperature to 600 degrees, high purity nitrogen protection, gas flow rate is 20 ml.min-1), wya Abbe refractometer.
In pyridine and KOH reflux for two hours, distillation, collected from 114 to 116 DEG C and anhydrous dichloromethane fraction; K2CO3 dry weight three [et3nh]cl, triethylamine hydrochloride steaming; phosphorus trichloride, aluminium chloride, sulfur powder is pure.
Tris(2-chloroethyl)phosphate(TCEP)
Appearance: Pure Tris (2-Chloroethyl) Phosphate Is A Colorless Or Pale Yellow Oily Transparent Liquid With A Light Creamy Taste.
Refractive Index (N20D) 1.4731
Boiling Point Of 194 ° C, Flash Point Of 225 ° C
Freezing Point -64 ℃
Decomposition Temperature 240-280 ℃
Viscosity 38-47 Centipoise (20 ° C)
Phosphorus Content Of 10.8%
Chlorine Content Of 37.3%, With The General Organic Solvents (Such As Alcohol, Ketones, Aromatics, Chloroform, Etc.) Compatible, Insoluble In Aliphatic Hydrocarbons, Almost Insoluble In Water, And Hydrolytic Stability Is Good, In Alkaline Solution In A Small Amount Of Decomposition, The No Obvious Corrosion Of The Product.
Tris(2-chloroethyl)phosphate(TCEP)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%.
Synthesis (1) the preparation of ionic liquid [et3nh]cl-2alcl3. In nitrogen atmosphere, 13.8g (0.1mol) three ethylamine hydrochloride was added into the flask, then 26.67g (0.2mol) was added slowly, and the aluminum chloride was stirred up. Then the ionic liquid [et3nh]cl-2alcl3 was added after stirring 3H.
(2) compound thiophenyl phosphonic acid two chlorine (3) synthesis [14] to P C L 3 (34.4 g, 0.25 m o l) and [e t 3N]] after the addition of 6.5 6.5 (benzene) to the reflux solution of "e t 3N"], after adding up, it continues to reflux at 78-80 degrees. The mixture is cold to room temperature, and the 30min is placed. Then the excess PCl3 was evaporated at 40 degrees C.
The residual liquid cooled to 30 DEG C, and then batch addition of 28.4g sulfur powder (0.0887mol), to ensure that the reaction temperature at 80 degrees celsius. After adding 80 centigrade, the reaction was 1.5h. After cooling the reactant, add petroleum ether to stir 30min. After the stirring is stopped, the solution is stratified, the upper layer is petroleum ether phase, and the lower layer is ionic liquid phase.
The petroleum ether is separated and collected, and the unreacted two chlorinated phosphine phosphine is removed with cold water and then dried with anhydrous CaCl2 and decompressed to evaporate petroleum ether. The distillates at 150 degrees centigrade at 1333 PA were collected, with a yield of 52%. The measured density D25 is 1.394 (g/ml), and the refractive index n25d is 1.6180 (literature value: d25=1.390, n25d=1.6178-1.6182).
(3) compound 2,4,8,10- four oxa -3,9- two -3,9- two -3,9- two phenyl sulfide phosphaspirocyclic [5.5] eleven alkanes (1) synthesis of pentaerythritol 1.4g (about 0.01mol) and 3.2ml (0.04mol) dispersed in 30ml pyridine in dichloromethane, the ice water bath and cooled to 0 DEG C, 4.2g (0.02mol) phenyl phosphine sulfide generation two acyl chloride (5ml dissolved in dichloromethane) under stirring drops. Continue the ice bath and stir 15min, and then slowly heat up to 55 C reflux reaction. TLC followed up the reaction process. After 5h, the reaction ended. After spin evaporation, the white powder was removed. The distilled water was washed for three times. The white powder was recrystallized by acetonitrile, and the yield was 1, the yield was 75%.
(4) synthetic compound 2 of compound 5,5- two methyl -2- phenyl -2- thiosulfate two oxo heterocyclane (2) is similar to 1. The yield is 68%.
The reaction of the preparation of 1 and 2 was carried out according to the SN2 process, and the polarity of the solvent was not beneficial to the reaction, so dichloromethane was selected as the solvent. Pyridine, as a compress, can absorb the HCl produced by the reaction very well and promote the positive reaction. Compared with the literature, acetonitrile is selected as the solvent for recrystallization in the post-processing, and the purity of the product is higher.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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