News Details
A new type of flame retardant for sulfur and phosphorus
2017-10-13 10:50:53
A new type of flame retardant for sulfur and phosphorus
New phosphorus-containing flame retardant sulfur by its unique quality of solid carbon and hand retention mechanisms and part of the gas flame retardant mechanism of the flame retardant process can not only reduce the heat release rate of material, improve the flame retardant effect, has overcome the phosphorus-containing flame retardant burns easily release irritating and corrosive halolide gases as well as the shortcoming of large amounts of toxic smoke, is one of the important development direction of flame retardant of research and development.
In research of new phosphorus-containing flame retardants in the process of sulfur, pentaerythritol was found a series of annular phosphonic acid ester polyols, such as synthetic than fat phosphonic acid ester has more excellent flame retardant efficiency, they have abundant carbon sources and acid source, the expansion type flame retardant plays an important role. A large number of studies have shown that the sulfur element is also an effective flame retardant element and has synergistic effect with phosphorus. The new type of sulfur - containing phosphor flame retardant has a great development.
Based on benzene, phosphorus trichloride, sulfur powder as raw material, through the friede - thio crafts synthesized phenyl phosphonic acid dichloride (3) (phenylphosphonothioic dichloride), glucosinolates phenyl phosphonic acyl chloride and pentaerythritol or new flame retardant neopentyl glycol synthesized 2,4,8,10 - four oxygen mixed - 3, 9 - disulfide - 3, 9 - diphenyl - 3, 9 - two phosphorus mixed spiro undecane
(1)(2,4,8,10-tetraoxa-3,9- diphenyl-3,9- diphenyl-3,9- diphenyl-3,9- diphenyl) -undecane) and 5,5- dimethyl-2-diphenyl - 2-2-2-2 - dioxophosphate
(2) (5, 5 - dimethyl - 2 - phenyl - 2 - thio - 1 31 - dioxaphosphorinane) (scheme 1). In the synthesis of phenylphosphonyl dichloride, the use of ionic liquid method was used to avoid the problem that the catalyst alcl3 could not be removed. The results of thermal performance indicate that compound 1 has good carbonicity and is a potential excellent flame retardant.
Bruker av400 MHZ type nuclear magnetic resonance instrument (dmso-d6 as solvent, TMS as internal standard); Perkin - Elmer 2000 ft-ir type infrared spectrometer (KBR press); DSC 204 f1 differential thermal scanning calorimeter.
209 f1 thermogravimetric heat - a laparoscope, usually connected to a differential thermal analyzer (10 ℃ temperature. Min - 1, temperature range for the room temperature to 600 ℃, high purity nitrogen protection, gas flow velocity of 20 ml. Min - 1); Wya abbe refractometer.
Isopropylphenyl Phosphate(IPPP35) Use
The Product Is Used For Rubber Products And PVC Plastic Flame Retardant Conveyor Belt, Cable, Chloroprene Rubber, Rubber And Other Synthetic Rubber Flame Retardant Plasticizer, Isopropylphenyl Phosphate Flame Retardant IPPP35 Use Also Applies To Fabric Coating, Circuit Boards, Flooring, Textiles, PVC, Phenolic Resin, And Other Fields.
Isopropylphenyl Phosphate Flame Retardant IPPP35 Halogen-Free Phosphate Flame Retardant Plasticizer, Which Does Not Pollute The Environment Twice. It Is The Lowest In The Phosphate Species And Has The Highest Phosphorus Content. This Product Is Colorless And Transparent, Good Compatibility, The Use Of Both Flame Retardant And Plasticizer, In The Flame Retardant And Plasticizer To Play A Balance Between The Role, But Also To Make The Processing Of The Same Material And Its Physical Properties.
Add koh back two hours to the pyridine, distillation, collected 114 ~ 116 ℃ fraction; Dichloromethane added anhydrous k2co3 dry resteaming; Triethylamine hydrochloride [et3nh] cl, phosphorus trichloride, aluminum chloride, and sulfur powder are all sold in the market.
The synthesis of (1) ionic liquid [et3nh]cl-2alcl3 prepared nitrogen atmosphere, adding 13.8g(0.1mol) triethylamine hydrochloride in the round bottom flask, and then slowly adding 26.67g(0.2mol) of anhydrous aluminum chloride, after stirring 3h, the ionic liquid was stirred.
Sulfur compounds (2) generation of phenyl phosphonic acyl chloride (3) the synthesis of to the 3 p c l (3, 4, 4 g, 0. 2, 5 m o l) and 3 n h] [e t c l - 2 alcl3 (3.08 g, 3.08 m mol) chase the backflow of drop join 6.5 g (0.0833 mol) benzene and 1 h to continue is finished in 78-80 ℃ reflux reaction 4 h. Chill mixture to room temperature for 30min. Then in 40 ℃ under reduced pressure steam pcl3 to excess.
The residual cools to 30 ℃, and partial add 28.4 g sulfur powder (0.0887 mol), to ensure that the reaction temperature at about 80 ℃. To continue after 80 ℃ under the reaction of 1.5 h. After cooling the reactants, add the petroleum ether and stir for 30min. After the agitation stops, the solution is layered, the upper layer is the petroleum ether phase, the lower layer is ionic liquid phase.
Separate collection of petroleum ether, wash and remove the unreacted phenyl dichloride with cold water, then dry with anhydrous cacl2 and decompress the petroleum ether. Collect 1333 pa under 150 ℃ fraction, the yield of 52%. The density of d25 was 1.394 (g/ml), and the refractive index n25d was 1.6180 (literature value: d25= 1.390, n25d= 1.6178-1.6182).
(3) compound 2,4,8,10 - four oxygen mixed - 3, 9 - disulfide - 3, 9 - diphenyl - 3, 9 - two phosphorus mixed spiro [5.5] undecane (1) the synthesis of the season will be 1.4 g e four (about 0.01 mol) and 0.01 ml pyridine (0.04 mol) dispersed in 30 ml methylene chloride, cool in the ice water bath to 0 ℃, the 4.2 g (0.02 mol) phenyl phosphonic and acyl chloride (dissolved in 5 ml methylene chloride) into under stirring. Never put off till tomorrow what you can continue to ice bath mixing 15 min, and then slowly heat up to 55 ℃ reflux reaction. TLC followed the reaction process, after 5h, the reaction was finished, and the rotary removal solvent, white powdery solid, distilled water was washed three times, with acetonitrile recrystallized white powder 1, yield 75%.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
New phosphorus-containing flame retardant sulfur by its unique quality of solid carbon and hand retention mechanisms and part of the gas flame retardant mechanism of the flame retardant process can not only reduce the heat release rate of material, improve the flame retardant effect, has overcome the phosphorus-containing flame retardant burns easily release irritating and corrosive halolide gases as well as the shortcoming of large amounts of toxic smoke, is one of the important development direction of flame retardant of research and development.
In research of new phosphorus-containing flame retardants in the process of sulfur, pentaerythritol was found a series of annular phosphonic acid ester polyols, such as synthetic than fat phosphonic acid ester has more excellent flame retardant efficiency, they have abundant carbon sources and acid source, the expansion type flame retardant plays an important role. A large number of studies have shown that the sulfur element is also an effective flame retardant element and has synergistic effect with phosphorus. The new type of sulfur - containing phosphor flame retardant has a great development.
Based on benzene, phosphorus trichloride, sulfur powder as raw material, through the friede - thio crafts synthesized phenyl phosphonic acid dichloride (3) (phenylphosphonothioic dichloride), glucosinolates phenyl phosphonic acyl chloride and pentaerythritol or new flame retardant neopentyl glycol synthesized 2,4,8,10 - four oxygen mixed - 3, 9 - disulfide - 3, 9 - diphenyl - 3, 9 - two phosphorus mixed spiro undecane
(1)(2,4,8,10-tetraoxa-3,9- diphenyl-3,9- diphenyl-3,9- diphenyl-3,9- diphenyl) -undecane) and 5,5- dimethyl-2-diphenyl - 2-2-2-2 - dioxophosphate
(2) (5, 5 - dimethyl - 2 - phenyl - 2 - thio - 1 31 - dioxaphosphorinane) (scheme 1). In the synthesis of phenylphosphonyl dichloride, the use of ionic liquid method was used to avoid the problem that the catalyst alcl3 could not be removed. The results of thermal performance indicate that compound 1 has good carbonicity and is a potential excellent flame retardant.
Bruker av400 MHZ type nuclear magnetic resonance instrument (dmso-d6 as solvent, TMS as internal standard); Perkin - Elmer 2000 ft-ir type infrared spectrometer (KBR press); DSC 204 f1 differential thermal scanning calorimeter.
209 f1 thermogravimetric heat - a laparoscope, usually connected to a differential thermal analyzer (10 ℃ temperature. Min - 1, temperature range for the room temperature to 600 ℃, high purity nitrogen protection, gas flow velocity of 20 ml. Min - 1); Wya abbe refractometer.
Isopropylphenyl Phosphate(IPPP35) Use
The Product Is Used For Rubber Products And PVC Plastic Flame Retardant Conveyor Belt, Cable, Chloroprene Rubber, Rubber And Other Synthetic Rubber Flame Retardant Plasticizer, Isopropylphenyl Phosphate Flame Retardant IPPP35 Use Also Applies To Fabric Coating, Circuit Boards, Flooring, Textiles, PVC, Phenolic Resin, And Other Fields.
Isopropylphenyl Phosphate Flame Retardant IPPP35 Halogen-Free Phosphate Flame Retardant Plasticizer, Which Does Not Pollute The Environment Twice. It Is The Lowest In The Phosphate Species And Has The Highest Phosphorus Content. This Product Is Colorless And Transparent, Good Compatibility, The Use Of Both Flame Retardant And Plasticizer, In The Flame Retardant And Plasticizer To Play A Balance Between The Role, But Also To Make The Processing Of The Same Material And Its Physical Properties.
Add koh back two hours to the pyridine, distillation, collected 114 ~ 116 ℃ fraction; Dichloromethane added anhydrous k2co3 dry resteaming; Triethylamine hydrochloride [et3nh] cl, phosphorus trichloride, aluminum chloride, and sulfur powder are all sold in the market.
The synthesis of (1) ionic liquid [et3nh]cl-2alcl3 prepared nitrogen atmosphere, adding 13.8g(0.1mol) triethylamine hydrochloride in the round bottom flask, and then slowly adding 26.67g(0.2mol) of anhydrous aluminum chloride, after stirring 3h, the ionic liquid was stirred.
Sulfur compounds (2) generation of phenyl phosphonic acyl chloride (3) the synthesis of to the 3 p c l (3, 4, 4 g, 0. 2, 5 m o l) and 3 n h] [e t c l - 2 alcl3 (3.08 g, 3.08 m mol) chase the backflow of drop join 6.5 g (0.0833 mol) benzene and 1 h to continue is finished in 78-80 ℃ reflux reaction 4 h. Chill mixture to room temperature for 30min. Then in 40 ℃ under reduced pressure steam pcl3 to excess.
The residual cools to 30 ℃, and partial add 28.4 g sulfur powder (0.0887 mol), to ensure that the reaction temperature at about 80 ℃. To continue after 80 ℃ under the reaction of 1.5 h. After cooling the reactants, add the petroleum ether and stir for 30min. After the agitation stops, the solution is layered, the upper layer is the petroleum ether phase, the lower layer is ionic liquid phase.
Separate collection of petroleum ether, wash and remove the unreacted phenyl dichloride with cold water, then dry with anhydrous cacl2 and decompress the petroleum ether. Collect 1333 pa under 150 ℃ fraction, the yield of 52%. The density of d25 was 1.394 (g/ml), and the refractive index n25d was 1.6180 (literature value: d25= 1.390, n25d= 1.6178-1.6182).
(3) compound 2,4,8,10 - four oxygen mixed - 3, 9 - disulfide - 3, 9 - diphenyl - 3, 9 - two phosphorus mixed spiro [5.5] undecane (1) the synthesis of the season will be 1.4 g e four (about 0.01 mol) and 0.01 ml pyridine (0.04 mol) dispersed in 30 ml methylene chloride, cool in the ice water bath to 0 ℃, the 4.2 g (0.02 mol) phenyl phosphonic and acyl chloride (dissolved in 5 ml methylene chloride) into under stirring. Never put off till tomorrow what you can continue to ice bath mixing 15 min, and then slowly heat up to 55 ℃ reflux reaction. TLC followed the reaction process, after 5h, the reaction was finished, and the rotary removal solvent, white powdery solid, distilled water was washed three times, with acetonitrile recrystallized white powder 1, yield 75%.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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