58.6 - 61.4%Spectr.; 14.6 - 15.3%Spectr. |
With ammonia; phosphorous acid;perfluoroundecanoic acid; In water; at 120℃; for 2h;Product distribution / selectivity; |
Example 3.; An ATMP composition was made by reacting the listed ingredients in the stated proportions. Reactant g mole(s) Phosphorous acid 47.71 0.5697 Ammonia (32 % solution) 10.08 0.1899 Formaldehyde (36.6 % solution) 49.03 0.5981 Perfluoro-undecanoic acid 12.50 0.02215 The perfluoro-undecanoic acid catalyst is immiscible in the reaction medium at the reaction conditions. All the reactants, except the formaldehyde, were charged into a pressure autoclave before starting the heating. The formaldehyde was added starting at a temperature of 120 C during a period of 2 hours. The reaction product, analyzed in accordance with the method of Example 1, contained the following major compounds. ATMP 58.6 % N-MeIBMPA 14.6 %H3PO3 14.4 %H3PO4 5.6 % Further aminopolymethylene phosphonic acid compositions were made by reacting the listed ingredients as set forth below. Reactant Example N g mole(s) Phosphorous acid 4 46.71 0.5697 Idem 5,6 93.43 1.1394 Perfluoroundecanoic acid 6 3.21 0.005697 Idem 5 6.42 0.01139 Idem 4 7.45 0.0132 Ammonia (32 % solution) 4 10.08 0.1899 Idem 5,6 20.17 0.3798 Formaldehyde (36.6 % sol.) 4 49.03 0.5981 Idem 5,6 98.04 1.1962 The reaction mixture was prepared by adding the phosphorous acid, the perfluoro undecanoic acid and the ammonia to the reactor under ambient conditions. The reaction mixture was then heated to 120 C and the formaldehyde was gradually added, starting from 120 C, over a period of 120 minutes. The reaction products analyzed in accordance with the method of Example 1 confirmed the formation of major levels of phosphonic acid components as follows. Example N ATMP-% N-MeIBMPA-%H3PO3-%H3PO4-% 4 61.4 15.3 9.2 6.6 5 59.2 15.0 8.3 6.8 6 59.0 15.1 8.4 6.7 The analytical results confirm the formation of high levels of desirable phosphonic acid compounds with the further observation that the reaction conditions offer ample leeway for optimization as is shown by the fairly substantial levels of non-reacted phosphorous acid and the concurrent decrease in the formation of phosphoric acid |
61 - 69.4%Spectr.; 6.7 - 7.6%Spectr. |
With ammonia; phosphorous acid;sodium hydrogen sulfate; In water; at 105℃; for 3.5 - 5h;Heating / reflux;Product distribution / selectivity; |
Additional aminopolyalkylene phosphonic acid preparations were carried out as described for Examples 4-8, except as specifically recited below. The listed ingredients were used, in Examples 9-13, in identical levels as follows. Reactant g mole(s) Phosphorous acid 452.03 5.5125 Ammonia (25 % solution) 122.4 1.8 Formaldehyde (36.6 % solution) 464.71 5.67 The levels and species of catalyst and added water were selected as follows. Example Catalyst Added Water Species g mole(s) g 9CH3SO3H 278.2 2.899 none 10NaHSO4 347.88 2.899 52.18 11CH3SO3H 278.2 2.899 none 12 idem 278.2 2.899 none 13H2SO4 294.4 2.899 none The reactants were added in the sequence of Example 1. The formaldehyde was added, starting from 105 C, over a period of: 1.5 hours - Examples 9, 10 and 11, and3 hours - Examples 12 and 13,under continuous distillation, at the reaction temperature. The reaction products, analyzed in accordance with Example 1, contained the listed products in the stated levels. Example %-ATMP %-Phosphorous acid %-N-MeIBMPA 9 78.3 10.6 3.8 10 69.4 13.5 6.7 11 77.7 10.3 3.5 12 75.7 11.3 3.1 13 72.2 8.5 3.2Aminopolymethylene phosphonic acids were prepared, in accordance with Example 1, having the following compositions. Reactant Example 14 15 16 17 Phosphorous acid - g 100.45 100.45 452.05 301.35 - mole 1.225 1.225 5.5125 3.67 Ammonia (25 % solution) - g 27.2 27.2 122.4 81.6 - mole 0.4 0.4 1.8 1.2 Formaldehyde (36.6 % solution) - g 103.27 103.27 464.7 309.8 -mole 1.26 1.26 5.67 3.77 Water added -g 30.0 58.07 none none The levels and species of catalysts used were as follows. Example Catalyst Species g mole(s) 14NaHSO4 77.28 0.644 15CF3COOH 45 0.3 16 Oxalic acid 260.9 2.899 17 p-Toluene sulfonic acid 332.41 1.93 The reactants were added in the sequence of Example 1. The formaldehyde was added starting from 105 C over a period of: 1.5 hours - Example 14:3 hours - Examples 16 and 17; and2 hours - Example 15.under continuous distillation as in Examples 9-13. The reaction products, analyzed as in Example 1, contained the following phosphonate components. Example %-ATMP %-Phosphorous acid %-N-MeIBMPA 14 61 21.2 7.6 15 65 21.9 4.9 16 57.3 17.7 14.1 17 70.7 16.3 4.2 |
60.0%Spectr.; 13.3%Spectr. |
With ammonia; phosphorous acid;oxalic acid; In water; at 125℃; for 2.5h;Heating / reflux;Product distribution / selectivity; |
Example 32. An aminopolymethylene phosphonic acid compound was prepared by reacting, in a closed vessel under autogeneous pressure built up, the listed ingredients in the manner described in Example 1. Reactant g/moles(s) Phosphorous acid 45.20/0.551 Methane sulfonic acid 13.48/0.140 Ammonia (32 % solution) 9.56/0.18 Formaldehyde (36.6 % solution) 46.47/0.567 10 % of the ammonia was added together with the other ingredients whereas the remaining 90 % of the ammonia was added together with the formaldehyde, starting from 105 C, over a period of 3 hours. The reaction product analyzed as in Example 1 contained the following compounds %-ATMP 55.3 %-N-MeIBMPA 4.6 %-Phosphorous acid 17.5 Additional aminopolymethylene phosphonic acids were prepared, Examples 33-46, by reacting, in a closed vessel under autogeneous pressure built up, the listed ingredients in the stated proportions, as set forth in Example 1. Reactant g/mole(s) Example Phosphorous acid 90.40/1.102 all Ammonia (32 % solution) 19.12/0.36 all Formaldehyde (36.6 % solution) 92.94/1.134 all Methane sulfonic acid 26.96/0.281 33-44 idem 29.38/0.306 45 idem 14.99/0.153 46 The formaldehyde/ammonia additions in the individual Examples were as follows. Examples 33 10 % of the ammonia was added at the start and 90 % was added with the formaldehyde over a period of 90 minutes starting from 115 C; 34 As in Example 33, except that 40 % of the ammonia was added at the start and the formaldehyde/ammonia reactant was added over a period of 30 minutes; As in Example 34, except that the formaldehyde/ammonia was added starting from 120 C; 36 As in Example 34 except that the formaldehyde/ammonia was added starting from 125 C; 37 As in Example 33, except that the formaldehyde/ammonia was added starting from 115 C over a period of 30 minutes; 38 As in Example 37, except that the formaldehyde/ammonia was added starting from 125 C; 39 As in Example 38, except that the formaldehyde/ammonia was added over a period of 30 minutes starting from 120 C; 40 As in Example 39, except that 30 % of the ammonia was added at the start while the remaining 70 % was added with the formaldehyde; 41 As in Example 37, except that 70 % of the ammonia was added at the start and 30 % with the formaldehyde; 42 As in Example 41, except that the formaldehyde/ammonia was added starting from 120 C; 43 As in Example 42, except that the formaldehyde/ammonia was added over a period of 3 minutes starting from 115 C; 44-46 As in Example 43, except that the formaldehyde/ammonia was added starting from 125 C. The reaction products, analyzed as in Example 1, contained the following phosphonate compounds. Example %-ATMP %-N-MeIBMPA%-H3PO3 33 63.0 4.9 14.3 34 69.2 6.4 13.2 35 70.8 6.0 9.5 36 69.1 5.9 8.6 37 68.1 6.4 10.9 38 64.2 5.5 9.3 39 67.2 6.2 10.2 40 72.4 6.0 8.7 41 72.9 6.5 10.8 42 72.3 5.7 9.5 43 68.7 9.2 12.7 44 70.9 8.3 10.4 45 70.7 8.1 11.4 46 68.3 10.4 10.0 A series of aminopolymethylene phosphonic acid compounds, Examples 47-59, were prepared in a closed vessel under autogeneous pressure built up thereby using the method of Example 1 with specific changes as follows. Reactants g/mole(s) Examples Phosphorous acid 90.40/1.102 47-53, 56 idem 67.80/0.827 54, 55, 57 idem 88.56/1.08 58, 59 Ammonia (32 % solution) 19.12/0.36 47-53, 56, 58, 59 idem 14.34/0.27 54, 55, 57 Formaldehyde (36.6 % solution) 92.94/1.134 47-53, 56, 58, 59 idem 69.70/0.85 54, 55, 57 The acid catalyst species were used in the listed proportions. Acid catalyst g/mole(s) Examples Methane sulfonic acid 20.73/0.216 53 idem 22.03/0.229 54 idem 25.92/0.27 55 idem 26.95/0.281 49-51, 56 idem 24.19/0.252 52 idem 2.64/0.028 59 idem 34.56/0.36 58 idem 31.10/0.344 57 Malonic acid 21.63/0.281 47 Oxalic acid 25.27/0.281 48 The operational sequence of the reaction was performed as set forth in Example 1, with modified conditions as follows. Example 47, 48 As in Example 1, except that 70 % of the ammonia was present at the start whereas 30 % of the ammonia was added together with the formaldehyde, starting from 125 C over a period of 30 minutes. 51-55 As in Example 47, except that the formaldehyde/ammonia was added starting from 145 C over a period of 3 minutes. 49, 50 As in Example 51, except that the formaldehyde/ammonia was added, starting from 135 C, Ex. 49., or 140 C, Ex. 50. 56, 57 As in Example 1, except that the formaldehyde was added in 3 minutes starting from 145 C. 58As in Example 1, except that 70 % of the H3PO3 was added with the formaldehyde, under mechanical stirring, starting from 125 C over a period of 3 minutes. 59 As in Example 1 except that the formaldehyde was added under stirring starting from 125 C over a period of 30 minutes. The reaction products, analyzed as in Example 1, showed the presence of phosphonate compounds as follows. Example %-ATMP %-N-MeIBMPA%-H3PO3 47 45.7 16.6 24.6 48 60.0 13.3 14.0 49 70.2 8.0 9.8 50 68.0 8.6 7.4 51 63.0 11.8 7.5 52 64.7 10.5 8.3 53 66.6 9.7 6.3 54 67.0 8.0 8.3 55 67.1 6.9 9.6 56 62.3 12.0 8.... |
57.3%Spectr.; 14.1%Spectr. |
With ammonia; phosphorous acid;oxalic acid; at 105℃; for 5h;Heating / reflux; Neat (no solvent);Product distribution / selectivity; |
Aminopolymethylene phosphonic acids were prepared, in accordance with Example 1, having the following compositions. Reactant Example 14 15 16 17 Phosphorous acid - g 100.45 100.45 452.05 301.35 - mole 1.225 1.225 5.5125 3.67 Ammonia (25 % solution) - g 27.2 27.2 122.4 81.6 - mole 0.4 0.4 1.8 1.2 Formaldehyde (36.6 % solution) - g 103.27 103.27 464.7 309.8 -mole 1.26 1.26 5.67 3.77 Water added -g 30.0 58.07 none none The levels and species of catalysts used were as follows. Example Catalyst Species g mole(s) 14NaHSO4 77.28 0.644 15CF3COOH 45 0.3 16 Oxalic acid 260.9 2.899 17 p-Toluene sulfonic acid 332.41 1.93 The reactants were added in the sequence of Example 1. The formaldehyde was added starting from 105 C over a period of: 1.5 hours - Example 14:3 hours - Examples 16 and 17; and2 hours - Example 15.under continuous distillation as in Examples 9-13. The reaction products, analyzed as in Example 1, contained the following phosphonate components. Example %-ATMP %-Phosphorous acid %-N-MeIBMPA 14 61 21.2 7.6 15 65 21.9 4.9 16 57.3 17.7 14.1 17 70.7 16.3 4.2 |
45.7%Spectr.; 16.6%Spectr. |
With ammonia; phosphorous acid;malonic acid; In water; at 125℃; for 2.5h;Heating / reflux;Product distribution / selectivity; |
Example 32. An aminopolymethylene phosphonic acid compound was prepared by reacting, in a closed vessel under autogeneous pressure built up, the listed ingredients in the manner described in Example 1. Reactant g/moles(s) Phosphorous acid 45.20/0.551 Methane sulfonic acid 13.48/0.140 Ammonia (32 % solution) 9.56/0.18 Formaldehyde (36.6 % solution) 46.47/0.567 10 % of the ammonia was added together with the other ingredients whereas the remaining 90 % of the ammonia was added together with the formaldehyde, starting from 105 C, over a period of 3 hours. The reaction product analyzed as in Example 1 contained the following compounds %-ATMP 55.3 %-N-MeIBMPA 4.6 %-Phosphorous acid 17.5 Additional aminopolymethylene phosphonic acids were prepared, Examples 33-46, by reacting, in a closed vessel under autogeneous pressure built up, the listed ingredients in the stated proportions, as set forth in Example 1. Reactant g/mole(s) Example Phosphorous acid 90.40/1.102 all Ammonia (32 % solution) 19.12/0.36 all Formaldehyde (36.6 % solution) 92.94/1.134 all Methane sulfonic acid 26.96/0.281 33-44 idem 29.38/0.306 45 idem 14.99/0.153 46 The formaldehyde/ammonia additions in the individual Examples were as follows. Examples 33 10 % of the ammonia was added at the start and 90 % was added with the formaldehyde over a period of 90 minutes starting from 115 C; 34 As in Example 33, except that 40 % of the ammonia was added at the start and the formaldehyde/ammonia reactant was added over a period of 30 minutes; As in Example 34, except that the formaldehyde/ammonia was added starting from 120 C; 36 As in Example 34 except that the formaldehyde/ammonia was added starting from 125 C; 37 As in Example 33, except that the formaldehyde/ammonia was added starting from 115 C over a period of 30 minutes; 38 As in Example 37, except that the formaldehyde/ammonia was added starting from 125 C; 39 As in Example 38, except that the formaldehyde/ammonia was added over a period of 30 minutes starting from 120 C; 40 As in Example 39, except that 30 % of the ammonia was added at the start while the remaining 70 % was added with the formaldehyde; 41 As in Example 37, except that 70 % of the ammonia was added at the start and 30 % with the formaldehyde; 42 As in Example 41, except that the formaldehyde/ammonia was added starting from 120 C; 43 As in Example 42, except that the formaldehyde/ammonia was added over a period of 3 minutes starting from 115 C; 44-46 As in Example 43, except that the formaldehyde/ammonia was added starting from 125 C. The reaction products, analyzed as in Example 1, contained the following phosphonate compounds. Example %-ATMP %-N-MeIBMPA%-H3PO3 33 63.0 4.9 14.3 34 69.2 6.4 13.2 35 70.8 6.0 9.5 36 69.1 5.9 8.6 37 68.1 6.4 10.9 38 64.2 5.5 9.3 39 67.2 6.2 10.2 40 72.4 6.0 8.7 41 72.9 6.5 10.8 42 72.3 5.7 9.5 43 68.7 9.2 12.7 44 70.9 8.3 10.4 45 70.7 8.1 11.4 46 68.3 10.4 10.0 A series of aminopolymethylene phosphonic acid compounds, Examples 47-59, were prepared in a closed vessel under autogeneous pressure built up thereby using the method of Example 1 with specific changes as follows. Reactants g/mole(s) Examples Phosphorous acid 90.40/1.102 47-53, 56 idem 67.80/0.827 54, 55, 57 idem 88.56/1.08 58, 59 Ammonia (32 % solution) 19.12/0.36 47-53, 56, 58, 59 idem 14.34/0.27 54, 55, 57 Formaldehyde (36.6 % solution) 92.94/1.134 47-53, 56, 58, 59 idem 69.70/0.85 54, 55, 57 The acid catalyst species were used in the listed proportions. Acid catalyst g/mole(s) Examples Methane sulfonic acid 20.73/0.216 53 idem 22.03/0.229 54 idem 25.92/0.27 55 idem 26.95/0.281 49-51, 56 idem 24.19/0.252 52 idem 2.64/0.028 59 idem 34.56/0.36 58 idem 31.10/0.344 57 Malonic acid 21.63/0.281 47 Oxalic acid 25.27/0.281 48 The operational sequence of the reaction was performed as set forth in Example 1, with modified conditions as follows. Example 47, 48 As in Example 1, except that 70 % of the ammonia was present at the start whereas 30 % of the ammonia was added together with the formaldehyde, starting from 125 C over a period of 30 minutes. 51-55 As in Example 47, except that the formaldehyde/ammonia was added starting from 145 C over a period of 3 minutes. 49, 50 As in Example 51, except that the formaldehyde/ammonia was added, starting from 135 C, Ex. 49., or 140 C, Ex. 50. 56, 57 As in Example 1, except that the formaldehyde was added in 3 minutes starting from 145 C. 58As in Example 1, except that 70 % of the H3PO3 was added with the formaldehyde, under mechanical stirring, starting from 125 C over a period of 3 minutes. 59 As in Example 1 except that the formaldehyde was added under stirring starting from 125 C over a period of 30 minutes. The reaction products, analyzed as in Example 1, showed the presence of phosphonate compounds as follows. Example %-ATMP %-N-MeIBMPA%-H3PO3 47 45.7 16.6 24.6 48 60.0 13.3 14.0 49 70.2 8.0 9.8 50 68.0 8.6 7.4 51 63.0 11.8 7.5 52 64.7 10.5 8.3 53 66.6 9.7 6.3 54 67.0 8.0 8.3 55 67.1 6.9 9.6 56 62.3 12.0 8.... |
74.6 - 78.3%Spectr.; 2.6 - 3.1%Spectr. |
With ammonia; phosphorous acid;methanesulfonic acid; at 105℃; for 3.5 - 5h;Heating / reflux; Neat (no solvent);Product distribution / selectivity; |
Example 1.; Aminotrimethylene phosphonic acid (ATMP) was prepared by reacting phosphorous acid, ammonia and formaldehyde in the presence of a methanesulfonic acid catalyst. The individual components were used in the recited proportions. Reactant g mole(s) Phosphorous acid 100.45 1.225 Methanesulfonic acid 15.43 0.161 Ammonia (25 % solution) 27.2 0.4 Formaldehyde (36.6 % solution) 103.27 1.26 Water 58.07 - The phosphorous acid was first added to the reactor followed by the water, the methanesulfonic acid and the ammonia. The reaction mixture so prepared was subsequently heated to 105 C at which temperature the gradual addition of the formaldehyde was started. The formaldehyde was added in a period of 2 hours. The reaction was, after the addition of the formaldehyde, continued under reflux conditions for a further period of 2 hours. The reaction product was analyzed by means of a 31P-NMR spectroscopic method. It was found that ATMP was formed with a yield of 59.1 %.Additional ATMP preparations were conducted thereby using the method set forth in Example 1 and conducting the reactions in accordance with that Example 1 except that the methanesulfonic acid catalysts were utilized in the following levels. Example g mole(s) 2 61.85 0.644 3 42.33 0.441 The reaction product formed, analyzed as described in Example 1, showed a yield of ATMP of Example 2 76.8 % Example 3 72.7 %. These Examples (1-3) demonstrate the unexpected benefits of the inventive technology and show that the aminopolymethylene phosphonic acids can be prepared under exclusion of hydrohalogenic reactants in a short cycle time and in high yields as compared to state-of-the-art methods using the PCl3 route. Example 1, in addition to containing 59.1 % ATMP, was found to contain 15.9 % N-methylimino bis(methylene phosphonic acid) (N-MeIBMPA) and 16.5 % phosphorous acid. Example 2 contained, in addition to 76.8 % ATMP, 6.8 % N-MeIBMPA and 9 % phosphorous acid. Example 3 contained, in addition to a high level of ATMP, 8.3 % N-MeIBMPA and 12 % phosphorous acid. The one-step reaction was, for all three examples, completed in about 4 hours as compared to a multi-step procedure lasting generally more than 6 hours, starting from phosphorus trichloride. ATMP samples were prepared thereby using the method in accordance with Example 1, except that the reaction was conducted under continuous distillation at the temperature of the reaction. The individual reactants, except the catalyst and the added water, were used, in Examples 4-8, in identical proportions as follows: Reactant g mole(s) Phosphorous acid 100.45 1.225 Ammonia (25 % solution) 27.2 0.4 Formaldehyde (36.6 % solution) 103.27 1.26 The methanesulfonic acid and the added water were used in the following levels. Example Added water Methane sulfonic acid g g mole(s) 4 36.45 61.85 0.644 5 none 61.85 0.644 6 40.4 42.33 0.441 7 58.07 15.46 0.161 8 58.07 30.92 0.322 The reactants were added in the sequence described in Example 1. The formaldehyde was added starting at 105 C over a period of 3 hours, Example 4, or 1.5 hours, Examples 5-B. The preparations of these Examples were conducted under continuous distillation of water, at the reaction temperature, thereby also eliminating a minimal amount of non-reacted formaldehyde. The reaction products were analyzed as in Example 1. The analytical results were as follows. Example %-ATMP %-Phosphorous acid %-N-MeIBMPA 4 69.4 18.6 2.7 5 74.6 13.3 2.6 6 67.9 20.4 3.5 7 64.6 18.1 8.4 8 67.7 20.4 3.9 The results illustrate the unusually significant benefits attached to the inventive technology, in particular, the high yields of aminopolyalkylene phosphonic acids formed in a short one-step reaction cycle under substantial exclusion of negatives attached to the state-of-the-art hydrochloric acid technology. It is particularly noteworthy that the distillate can be recycled/used without an additional purification step as is required in the presence of hydrochloric acid. Particular attention is also drawn to the substantial absence of methylchloride, especially in the gaseous by-products. Additional aminopolyalkylene phosphonic acid preparations were carried out as described for Examples 4-8, except as specifically recited below. The listed ingredients were used, in Examples 9-13, in identical levels as follows. Reactant g mole(s) Phosphorous acid 452.03 5.5125 Ammonia (25 % solution) 122.4 1.8 Formaldehyde (36.6 % solution) 464.71 5.67 The levels and species of catalyst and added water were selected as follows. Example Catalyst Added Water Species g mole(s) g 9CH3SO3H 278.2 2.899 none 10NaHSO4 347.88 2.899 52.18 11CH3SO3H 278.2 2.899 none 12 idem 278.2 2.899 none 13H2SO4 294.4 2.899 none The reactants were added in the sequence of Example 1. The formaldehyde was added, starting from 105 C, over a period of: 1.5 hours - Examples 9, 10 and 11, and3 hours - Examples 12 and 13,under continuous distillation, at the reaction temperature. The reaction products, analyzed in accordanc... |
53.7%Spectr.; 17.6%Spectr. |
With ammonia; phosphorous acid;benzene-1,2-dicarboxylic acid; In water; at 125℃; for 2.5h;Heating / reflux;Product distribution / selectivity; |
Additional aminotrimethylene phosphonic acid compounds, Examples 65-67, were prepared by reacting the listed ingredients in the stated proportions thereby applying the sequence set forth in Example 1. Reactant g mole(s) Phosphorous acid 68.88 0.84 Water 10.0 Ammonia (32 % solution) 14.87 0.28 Formaldehyde (36.6 % solution) 72.3 0.882 The acid catalyst was used in the following proportions. Catalyst Example N g mole(s) Methanesulfonic acid 65 2.016 0.021 Methanesulfonic acid 66 10.08 0.105 Ortho-phthalic acid 67 46.51 0.28 The reactants, except the formaldehyde, were added to the reactor at the start at room temperature. This reaction mixture was then heated to 125 C at which temperature the gradual addition over a period of 30 minutes of the formaldehyde was started. The reaction was conducted in a closed vessel under autogeneous pressure built up. The reaction products, analyzed thereby using the method of Example 1, showed that the following compounds were formed. Example %-ATMP %-N-MeIBMPA%-H3PO3 %-H3PO4 65 54.5 18.4 12.7 7.4 66 67.4 9.5 11.4 3.1 67 53.7 17.6 13.0 7.0The results demonstrate benefits attached to the claimed technology, in particular the high yields obtained during a short, compared to conventional manufacturing methods, cycle with the further observation that there is ample room for optimizing the method considering the fairly substantial levels of un-reacted phosphorous acid. |
72.2%Spectr.; 3.2%Spectr. |
With ammonia; phosphorous acid;sulfuric acid; at 105℃; for 5h;Heating / reflux; Neat (no solvent);Product distribution / selectivity; |
Example 1.; Aminotrimethylene phosphonic acid (ATMP) was prepared by reacting phosphorous acid, ammonia and formaldehyde in the presence of a methanesulfonic acid catalyst. The individual components were used in the recited proportions. Reactant g mole(s) Phosphorous acid 100.45 1.225 Methanesulfonic acid 15.43 0.161 Ammonia (25 % solution) 27.2 0.4 Formaldehyde (36.6 % solution) 103.27 1.26 Water 58.07 - The phosphorous acid was first added to the reactor followed by the water, the methanesulfonic acid and the ammonia. The reaction mixture so prepared was subsequently heated to 105 C at which temperature the gradual addition of the formaldehyde was started. The formaldehyde was added in a period of 2 hours. The reaction was, after the addition of the formaldehyde, continued under reflux conditions for a further period of 2 hours. The reaction product was analyzed by means of a 31P-NMR spectroscopic method. It was found that ATMP was formed with a yield of 59.1 %.Additional ATMP preparations were conducted thereby using the method set forth in Example 1 and conducting the reactions in accordance with that Example 1 except that the methanesulfonic acid catalysts were utilized in the following levels. Example g mole(s) 2 61.85 0.644 3 42.33 0.441 The reaction product formed, analyzed as described in Example 1, showed a yield of ATMP of Example 2 76.8 % Example 3 72.7 %. These Examples (1-3) demonstrate the unexpected benefits of the inventive technology and show that the aminopolymethylene phosphonic acids can be prepared under exclusion of hydrohalogenic reactants in a short cycle time and in high yields as compared to state-of-the-art methods using the PCl3 route. Example 1, in addition to containing 59.1 % ATMP, was found to contain 15.9 % N-methylimino bis(methylene phosphonic acid) (N-MeIBMPA) and 16.5 % phosphorous acid. Example 2 contained, in addition to 76.8 % ATMP, 6.8 % N-MeIBMPA and 9 % phosphorous acid. Example 3 contained, in addition to a high level of ATMP, 8.3 % N-MeIBMPA and 12 % phosphorous acid. The one-step reaction was, for all three examples, completed in about 4 hours as compared to a multi-step procedure lasting generally more than 6 hours, starting from phosphorus trichloride. ATMP samples were prepared thereby using the method in accordance with Example 1, except that the reaction was conducted under continuous distillation at the temperature of the reaction. The individual reactants, except the catalyst and the added water, were used, in Examples 4-8, in identical proportions as follows: Reactant g mole(s) Phosphorous acid 100.45 1.225 Ammonia (25 % solution) 27.2 0.4 Formaldehyde (36.6 % solution) 103.27 1.26 The methanesulfonic acid and the added water were used in the following levels. Example Added water Methane sulfonic acid g g mole(s) 4 36.45 61.85 0.644 5 none 61.85 0.644 6 40.4 42.33 0.441 7 58.07 15.46 0.161 8 58.07 30.92 0.322 The reactants were added in the sequence described in Example 1. The formaldehyde was added starting at 105 C over a period of 3 hours, Example 4, or 1.5 hours, Examples 5-B. The preparations of these Examples were conducted under continuous distillation of water, at the reaction temperature, thereby also eliminating a minimal amount of non-reacted formaldehyde. The reaction products were analyzed as in Example 1. The analytical results were as follows. Example %-ATMP %-Phosphorous acid %-N-MeIBMPA 4 69.4 18.6 2.7 5 74.6 13.3 2.6 6 67.9 20.4 3.5 7 64.6 18.1 8.4 8 67.7 20.4 3.9 The results illustrate the unusually significant benefits attached to the inventive technology, in particular, the high yields of aminopolyalkylene phosphonic acids formed in a short one-step reaction cycle under substantial exclusion of negatives attached to the state-of-the-art hydrochloric acid technology. It is particularly noteworthy that the distillate can be recycled/used without an additional purification step as is required in the presence of hydrochloric acid. Particular attention is also drawn to the substantial absence of methylchloride, especially in the gaseous by-products. Additional aminopolyalkylene phosphonic acid preparations were carried out as described for Examples 4-8, except as specifically recited below. The listed ingredients were used, in Examples 9-13, in identical levels as follows. Reactant g mole(s) Phosphorous acid 452.03 5.5125 Ammonia (25 % solution) 122.4 1.8 Formaldehyde (36.6 % solution) 464.71 5.67 The levels and species of catalyst and added water were selected as follows. Example Catalyst Added Water Species g mole(s) g 9CH3SO3H 278.2 2.899 none 10NaHSO4 347.88 2.899 52.18 11CH3SO3H 278.2 2.899 none 12 idem 278.2 2.899 none 13H2SO4 294.4 2.899 none The reactants were added in the sequence of Example 1. The formaldehyde was added, starting from 105 C, over a period of: 1.5 hours - Examples 9, 10 and 11, and3 hours - Examples 12 and 13,under continuous distillation, at the reaction temperature. The reaction products, analyzed in accordanc... |
62.7%Spectr.; 8.4%Spectr. |
With ammonia; phosphorous acid;Amberlyst 15; In water; at 105℃; for 2.5h;Product distribution / selectivity; |
Example 2.; Further amino polymethylene phosphonic acids were prepared by reacting in the operational sequence of Example 1, except for the duration of the formaldehyde addition, the listed materials as follows: Reactant g mole(s) Phosphorous acid 100.45 1.225 Amberlyst 15 wet resin 125.0 Ammonia (25 %-solution) 27.2 0.4 Formaldehyde (36.6 %-solution) 103.27 1.26 The formaldehyde was added, starting from 105 C, under distillation, over a period of 2 hours and 30 minutes. The reaction product analyzed thereby using the method of Example 1 showed the following major component levels. ATMP 62.7 %; N-MeIBMPA 8.4 %; andH3PO3 21.1 %. |
57 - 67.5%Spectr.; 6.3 - 9.7%Spectr. |
With ammonia; phosphorous acid;Amberlyst 36; In water; at 20 - 125℃; for 1 - 4.33333h;Product distribution / selectivity; |
Example 1. Aminopolymethylene phosphonic acid compounds were prepared by reacting the listed ingredients in the stated proportions. Reactant g mole(s) Phosphorous acid 301.35 3.675 Amberlyst 36 dry 150.0 Ammonia (25 %-solution) 81.6 1.2 Formaldehyde (36.6 %-solution) 309.9 3.78 A mixture of the phosphorous acid, the Amberlyst 36 and the ammonia is heated up, under stirring, to 105 C starting from which temperature the formaldehyde was gradually added, under distillation, over a period of 4 hours and 20 minutes. The reaction product was analyzed with a 31P-NMR spectroscopic method. It was found that major levels of aminotrimethylene phosphonic acid (ATMP) and N-methyleneimino bis(methylene phosphonic acid) (N-MeIBMPA) were present in the reaction product, as follows: ATMP 67.5 %; N-MeIBMPA 6.3 %; andH3PO3 15.9 %. Example 7. 114 g Commercial wet Amberlyst 36 resin containing on average 56 % of water was soaked several times with 100 g of a solution of 87.14 % phosphorous acid in water, each time the soaked resin is agitated for 15 minutes followed by separating the aqueous phase and replacing it with a fresh solution of phosphorous acid. This soaking step was repeated three times and the Amberlyst resin so obtained was found to contain a mixture of 52.37 g of phosphorous acid and 11.46 g of water. Inasmuch as in this method, we need 67.80 g of phosphorous acid, 15.43 g of H3PO3 were added to thus complement the quantity present in the catalyst. The phosphorous acid ingredient was added to the Amberlyst catalyst followed by stirring the mixture at room temperature under addition of 14.34 g of ammonia (32 % solution). To this mixture was subsequently added, under agitation in a pressure autoclave starting at 125 C during a period of 60 minutes, 69.70 g, (0.8505 mole), of formaldehyde (36.6 % solution). The resin is thereafter separated, from the reaction mixture, by filtration and can be used as such as a catalyst in the following Example.Example 8. The recycled catalyst of Example 8 was mixed, at room temperature, with 67.8 g, (0.8268 mole), of phosphorous acid and 14.34 g, (0.8505 mole), of ammonia (32 % solution). 69.70 g, (0.8505 mole), of formaldehyde (36.6 % solution) were added to that mixture, in a pressure autoclave over a period of 60 minutes starting at 125 C. The reaction products of Examples 7 and 8, analyzed in accordance with the method of Example 1, showed that major levels of phosphonic acids were formed as follows. Example N ATMP-% N-MeIBMPA-%H3PO3-%H3PO4-% 7 57 9.5 12 3 8 57.4 9.7 12.3 3.4 |