tris(2-chloroethyl) phosphate

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl)phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl)phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl) phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl)phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl)phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methanol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A vessel fitted with stirrer, thermometer, heating mantle, and vertical reflux condenser was charged with 5308 g(42.8 moles) of dimethyl methylphosphonate, 5710 g. (20 moles) of tris(2-chloroethyl)phosphate, and 40 g. of anhydrous sodium carbonate. After a brief nitrogen purge to remove air (and thus avoid possible oxidative color development the reaction mixture was raised to 135°, at which point methyl chloride began to be evolved from the condenser outlet. Over five hours the temperature was gradually raised to 185° and held for 27 hours at which time measurement of the rate of methyl chloride evolution showed the rate to have dwindled to 0.08 cc/min. At this point, weighing the remaining reaction mixture showed that a weight loss of 3044 g. had occurred, corresponding to 60.3 moles of methyl chloride (as against a theoretical loss of 60 moles). While stirring was continued, the reactor was allowed to cool to about 92° under dry nitrogen. Then 282 g. (8.8 moles) of methanol was added over 5 minutes. This quantity was a small excess over the calculated amount of cyclic glycol ester, 7.8 moles, which had been determined to be present by the fact that a sample held for 10 minutes in water and then titrated with 0.1-N NaOH to Bromphenol blue end point showed 1.14 millequivalents of acid plus cyclic ester per gram, whereas a titration of a sample in methanol with methanolic 0.1-N KOH to Bromphenol blue showed 0.16 milliequivalents of acid per gram; thus 0.98 milliequivalents of cyclic glycol ester per gram was present by this assay method. The reaction mixture was heated for 2 hours at 95°, at which point the two titration results were 0.27 meg. acid plus cyclic ester per gram and 0.17 meq. acid per gram; thus only 0.10 meq. cyclic ester per gram remained by this assay method. At this point, a fast stream of ethylene oxide was introduced with stirring at 95°. After 4 hours, the titrations by both the aqueous and alcoholic method were nil. Heating was then stopped, ethylene oxide continued as the temperature drifted down to 80°, then vigorous nitrogen sparging was conducted at 90°-95° until dissolved volatiles were removed (found to be mostly dimethyl methylphosphonate). The weight change during this devolatilization step was 3.5%. To remove final traces of acid, which reformed in the devolatilization step, the batch was briefly retreated with ethylene oxide at 95°. Alternatively, 12 of the non-volatile diepoxide of cyclohexenylmethyl cyclohexenylcarboxylate was added. The product, by the ethylene oxide finishing method, had the following characteristics: A vessel fitted with stirrer thermometer, heating mantle After a brief nitrogen purge to remove air (and thus avoid possible oxidative color development the reaction mixture was raised to 135°, at which Over five hours the temperature was gradually raised to 185° the remaining reaction mixture to cool to about 92° under dry nitrogen The reaction mixture was heated for 2 hours at 95°, at which point the two titration results with stirring at 95° After 4 hours Heating drifted down to 80° was conducted at 90°-95° until dissolved volatiles were removed ( To remove final traces of acid, which was briefly retreated with ethylene oxide at 95° Alternatively, 12 of the non-volatile diepoxide of cyclohexenylmethyl cyclohexenylcarboxylate was added

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl)phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methanol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A vessel fitted with stirrer, thermometer, heating mantle, and vertical reflux condenser was charged with 5308 g(42.8 moles) of dimethyl methylphosphonate, 5710 g. (20 moles) of tris(2-chloroethyl)phosphate, and 40 g. of anhydrous sodium carbonate. After a brief nitrogen purge to remove air (and thus avoid possible oxidative color development the reaction mixture was raised to 135°, at which point methyl chloride began to be evolved from the condenser outlet. Over five hours the temperature was gradually raised to 185° and held for 27 hours at which time measurement of the rate of methyl chloride evolution showed the rate to have dwindled to 0.08 cc/min. At this point, weighing the remaining reaction mixture showed that a weight loss of 3044 g. had occurred, corresponding to 60.3 moles of methyl chloride (as against a theoretical loss of 60 moles). While stirring was continued, the reactor was allowed to cool to about 92° under dry nitrogen. Then 282 g. (8.8 moles) of methanol was added over 5 minutes. This quantity was a small excess over the calculated amount of cyclic glycol ester, 7.8 moles, which had been determined to be present by the fact that a sample held for 10 minutes in water and then titrated with 0.1-N NaOH to Bromphenol blue end point showed 1.14 millequivalents of acid plus cyclic ester per gram, whereas a titration of a sample in methanol with methanolic 0.1-N KOH to Bromphenol blue showed 0.16 milliequivalents of acid per gram; thus 0.98 milliequivalents of cyclic glycol ester per gram was present by this assay method. The reaction mixture was heated for 2 hours at 95°, at which point the two titration results were 0.27 meg. acid plus cyclic ester per gram and 0.17 meq. acid per gram; thus only 0.10 meq. cyclic ester per gram remained by this assay method. At this point, a fast stream of ethylene oxide was introduced with stirring at 95°. After 4 hours, the titrations by both the aqueous and alcoholic method were nil. Heating was then stopped, ethylene oxide continued as the temperature drifted down to 80°, then vigorous nitrogen sparging was conducted at 90°-95° until dissolved volatiles were removed (found to be mostly dimethyl methylphosphonate). The weight change during this devolatilization step was 3.5%. To remove final traces of acid, which reformed in the devolatilization step, the batch was briefly retreated with ethylene oxide at 95°. Alternatively, 12 of the non-volatile diepoxide of cyclohexenylmethyl cyclohexenylcarboxylate was added. The product, by the ethylene oxide finishing method, had the following characteristics: A vessel fitted with stirrer thermometer, heating mantle After a brief nitrogen purge to remove air (and thus avoid possible oxidative color development the reaction mixture was raised to 135°, at which Over five hours the temperature was gradually raised to 185° the remaining reaction mixture to cool to about 92° under dry nitrogen The reaction mixture was heated for 2 hours at 95°, at which point the two titration results with stirring at 95° After 4 hours Heating drifted down to 80° was conducted at 90°-95° until dissolved volatiles were removed ( To remove final traces of acid, which was briefly retreated with ethylene oxide at 95° Alternatively, 12 of the non-volatile diepoxide of cyclohexenylmethyl cyclohexenylcarboxylate was added

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl) phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90 - 100° until substantially neutral. The product was useful as a flame retardant at 5 - 10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: However, phosphorus trichloride can easily be oxidized by oxygen or oxygen-containing gases to phosphorus oxychloride. A slow, steady increase in the phosphorus oxychloride content can be observed during storage, transport and use of phosphorus trichloride. The phosphorus oxychloride lowers the quality of the phosphorus trichloride and necessarily leads to undesirable by-products during chemical processing, so that the desired end product is of lower quality and is obtained in a lesser yield. For example, in further processing to phosphorus pentachloride or phosphorus sulfochloride, all the phosphorus oxychloride reaches the end product. Because of the physical properties, subsequent separation is much more difficult than separation from phosphorus trichloride. During further processing to phosphorous acid, phosphoric acid is formed from the phosphorus oxychloride and phosphates are formed as by-products during the reaction with alcohols to phosphites. During the synthesis of tri-(2-chloroethyl) phosphite by reaction with ethylene oxide, tri-(2-chloroethyl) phosphate is formed as an interfering by-product.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: However, phosphorus trichloride can easily be oxidized by oxygen or oxygen-containing gases to phosphorus oxychloride. A slow, steady increase in the phosphorus oxychloride content can be observed during storage, transport and use of phosphorus trichloride. The phosphorus oxychloride lowers the quality of the phosphorus trichloride and necessarily leads to undesirable by-products during chemical processing, so that the desired end product is of lower quality and is obtained in a lesser yield. For example, in further processing to phosphorus pentachloride or phosphorus sulfochloride, all the phosphorus oxychloride reaches the end product. Because of the physical properties, subsequent separation is much more difficult than separation from phosphorus trichloride. During further processing to phosphorous acid, phosphoric acid is formed from the phosphorus oxychloride and phosphates are formed as by-products during the reaction with alcohols to phosphites. During the synthesis of tri-(2-chloroethyl) phosphite by reaction with ethylene oxide, tri-(2-chloroethyl) phosphate is formed as an interfering by-product.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 571 g. of tris(2-chloroethyl) phosphate and 531 g. of dimethyl methylphosphonate was heated at 181°-197° C. until 287.5 of methylchloride was evolved; this required 26 hours. The product was then heated at 95° with 28.2 g. of methenol, and finally treated with ethylene oxide at 90°-100° until substantially neutral. The product was useful as a flame retardant at 5-10 phr. in a styrenated polyester. A mixture of 571 g 26 hours The product was then heated at 95° with 28.2 g