Process for manufacturing crystal form II solid ammonium polyphosphate

Abstract: Long chain ammonium polyphosphate (crystal form II) is obtained by a reaction at temperatures between 180 º C and 200 º C using as raw materials phosphorous pentoxide (P₂O₅), diammonium orthophosphate ((NH₄)₂HPO₄) and ammonium sulphate ((NH₄)₂SO₄) in an atmosphere of ammonia gas. The manufacturing process here described allows to obtain a product which, after being cooled and milled, presents the following characteristics : a) a water solubility at 25 º C lower than 0.4 gr. per 100 ml. suspension; b) a viscosity of 10% by weight aqueous suspension lower than 40 cp. at 25 o C.; c) a viscosity of 30% by weight linear polyesther lower than 35,000 cp. at 25 o C. The product obtained by the present manufacturing process notably improves the characteristics of other commercial products and it is considered to be satisfactory for its application in intumescent paints and flame retarded plastics.

Description: Field of the invention The present invention refers to an industrial manufacturing process by means of which an ammonium polyphosphate (APP) of the crystal form II type, characterized by its low solubility in water and its low viscosity in aqueous and organic suspensions, is obtained. The ammonium polyphosphate, generic chemical formula (NH 4 PO 3 ) n being n>10, presents different crystalline forms depending on the raw materials and the manufacturing process used. There are several patents describing other manufacturing processes for APP: European patents EP 0 088 264 and EP 0 049 763, German patents DE P2330174.8 and DE P767655.0 and U.S. patent US 3,912,802. Description of the prior art As it is widely known, solid ammonium polyphosphate has been used as flame retardant additive for several decades in the paints and plastics industries. The current increase of applications in both industrial sectors has required an important effort in improving the quality of the raw materials and additives involved in the manufacturing of products. One of these additives is ammonium polyphosphate. The present invention does not pretend to improve the well-known APP flame retardant properties, intrinsicly related to its chemical structure and composition, but points to the improvement of the physical properties of APP in order to perform better when added in the earlier mentioned fields. Two of these physical properties are water solubility and viscosity in both aqueous and organic media suspensions. For its application in intumescent paints, APP water solubility has to be as low as possible, since paints exposed to the weather are in permanent contact with the humidity of the air. The more soluble product the more tendency to be hidrolized and converted into ammonium orthophosphate which is a highly water soluble product, and consequently the paint looses its intumescent capacity somehow. Referring to the water viscosity, it is important that the addition of APP in water based paints does not increase its viscosity. A high value of the latter makes its application difficult. As a raw material for flame retarding plastics, it is preferred to use additives that do not modify the original physical properties of the material. In the field of polyolefines, for example, it is suitable that APP presents a very good thermal stability in order to avoid problems in the extrusion process. Regarding polyurethanes, when APP is formulated together with the polyol, it is important to have a low value of viscosity, specially when using diethylenglycol polyadipate, since a high viscosity would run into difficulties when handling the polyol. The European patent EP 0 088 265 describes a manufacturing process for APP where P 2 0 5 and (NH 4 ) 2 HP0 4 are mixed in an equimolecular ratio in ammonia atmosphere at a temperature range between 100°C and 250°C. According to this process, a product characterized by a solubility in water of 0,8 g/100 ml of suspension and a viscosity in 10% by weight water suspension of 100 mPa.s (= 100 cp) is obtained. As described in example 1 of the referred patent, the thermal gradient of the process makes it necessary to mantain in the plant a cooling system for the heating fluid or to carry out the polymerization reaction in two different steps, since the last phase of the reaction is carried out at more than 200°C and the initial phase starts at 100°C. Description of the invention According to the present invention the proposal improves the European Patent EP 0 088 265 not only in the product quality but also in energy savings in the process. Thus, in the process described in the present invention, the following raw materials are used: Phosphorous pentoxide and diammonium orthophosphate in equimolecular ratio. Ammonium sulphate in a proportion with regard to the former mixture between 0,5 and 5% by weight. A stochiometric excess of ammonia gas between 3 and 5% with regard to the initial mixture. The manufacturing process, according to the invention, presents the following steps: a) a previous mixing step of the solid raw materials. Duration between 5 and 10 minutes; b) a second step of polymerization reaction between 15 and 45 minutes with injection of ammonia gas. Maximum reactor pressure between 490-980 Pa (= 50-100 mm.w) at a temperature between 180°C and 200°C; c) a short homogeneization step without ammonia supply. Duration between 0 and 10 minutes; d) a final step of polimerization-neutralization between 2 and 4 hours with a supply of ammonia gas at a temperature range of 200°C-220°C and a minimum reactor pressure between 0 and 980 Pa (= 0-100 mm.w). The resulting product is unloaded from the reactor to a cooler and then milled in order to achieve the desired particle size. The ammonium polyphosphate (crystal form II) obtained by this procedure, shows the following characteristics: a) a 10% by weight water solution solubility less than 0,4 g/100 ml suspension. b) a maximum viscosity in 10% by weight water suspension of 40 mPa.s (= 40 cp). c) a maximum viscosity in 30% by weight polypropylenglycol suspension of 500 mPa.s (= 500 cp). d) a maximum viscosity in 30% by weight diethylenglycol polyadipate of 35.000 mPa.s (= 35.000 cp). Furthermore, the product satisfies the following technical specifications: % Crystal form II 99% minimum % P 2 0 5 total 71% minimum % N total 14% minimum pH (10% aqueous sol.) 5 minimum The ammonium polyphosphate obtained by the described process can be considered an optimum product for the application in paints as intumescent catalyst and in plastics as flame retardant additive. In conclusion it improves notably the product presented in the European patent EP 0 088 625. Application examples of the manufacturing process The following example 1 serve to illustrate the present invention. Example 2 and 3 are comparative. Example 1 200 kg of P 2 0 5 (1,41 Kmol), 186 kg of (NH 4 ) 2 HP0 4 (1,41 Kmol) and 5 kg of (NH 4 ) 2 SO 4 (37,88 mol) are mixed for 5 minutes at 200°C. The mixing is carried out in a preheated reactor of service capacity equal to 0,5 m 3 , provided with agitation and external heating by thermal fluid. Next it is supplied for 30 minutes with ammonia gas at a maximum pressure in the reactor of 980 Pa (= 100 mm.w). The average flow, controlled by an automatic valve, is 15 m 3 /h. In this phase of the reaction, the maximum power consumption is 70 amperes. The mixture is homogeneized for 8 minutes. Then, it is fed ammonia gas in two steps of two hours and 1 hour 45 minutes. The average flow for each step is 7,5 m 3 /h and 5 m 3 /h. The temperature of this phase of the reaction is 220°C. The total supply of ammonia gas is 32,5 m 3 (N.C.), which means a molar excess of 3,1 %. The operation takes place in a total period of 4 hours and 28 minutes. Example 2 The procedure is the same as explained in the example 1, however ammonium sulphate has not been added as raw material. The product obtained presents solubility and viscosity higher than the one in example 1 (see results in the comparative table). Example 3 (Comparable to the example 1 of the European patent EP 0 088 625) 200 kg of P 2 0 5 (1,41 Kmol) and 186 kg of (NH 4 ) 2 HP0 4 (1,41 Kmol) are mixed at 100°C in the same reactor as described in the example 1. For 25 minutes it is supplied 100 m 3 of ammonia gas with a maximum pressure in the reactor of 1.470 Pa (= 150 mm.w). Then, the mixture is homogenizated in nitrogen atmosphere (150 l/min.) for 35 minutes. In a period of 2 hours, it is supplied 14 m 3 of ammonia gas. The power consumption reaches 100 amperes in this phase of the reaction. The last step is carried out with the supply of 10 m 3 of ammonia gas at 230°C and atmospheric pressure. The total NH 3 supply is 34 m 3 (N.C.), which means a molar excess of 7,4%. The operation takes place in 5 hours. The ammonium polyphosphate so obtained has lower quality than the product resulting from example 1, as shown in the results of the comparative table. Procedure characteristics Example 1 Example 2 (Comparative) Example 3 (Comparative) Initial temperature (°C) 200 200 100 Final temperature (°C) 220 220 230 Max. reactor pressure (Pa) 980 980 1.470 Max. reactor pressure (mm.w) 100 100 150 Min. reactor pressure (Pa) 19,6 29,4 -196 Min. reactor pressure (mm.w) 2 3 -20 Max. power consumption (A) 70 75 100 Total time (hours) 4,47 4,47 5 Consumption of NH 3 (Nm 3 ) 32,50 32,50 34 Product characteristics pH (10% by w. in water) 5,5 5,6 5,8 Solubility (g/100 ml w.) 0,21 0,62 0,48 Viscosity (10% by w. in water) (mPa.s = cp) 18 59 46 Viscosity (30% by w. in polypropylenglicol) (mPa.s = cp) 438 446 470 Viscosity (30% by w. in diethylenglycol polyadipate) (mPa.s = cp) 25.000 32.000 38.000

Claims: Manufacturing process of long chain ammonium polyphosphate of crystal form II using as raw materials phosphorous pentoxide (P 2 0 5 ), diammonium orthophosphate ((NH 4 ) 2 HP0 4 ) and ammonium sulphate ((NH 4 ) 2 SO 4 ) in a molar ratio 1/1/0,01-0,08 in ammonia gas atmosphere (NH 3 ), following these steps: a) initial mixing step of solid raw materials for a period of time between 5 and 10 minutes; b) a second step of polymerisation reaction between 15 and 45 minutes with a supply of ammonia gas at a maximum reactor pressure of 490-980 Pa (= 50-100 mm.w) and at a minimum temperature of 180°C - 200°C.; c) a short homogenization step without ammonia supply; duration between 0 and 10 minutes; d) a final step between 2 and 4 hours with a supply of ammonia gas at a temperature range of 200°C-220°C and a minimum reactor pressure between 0 and 980 Pa (= 0-100 mm.w); the maximum thermal gradient of the process is 40°C and the molar excess of ammonia gas has a maximum value of 5%. Ammonium polyphosphate of crystal form II, obtained by the process of claim 1, which presents the following characteristics: a) solubility in 10% by weight APP water suspension less than 0,4 g APP/100 ml suspension; b) maximum viscosity in water (10% suspension) of 40 mPa.s (= 40 cp); c) maximum viscosity in polypropylenglycol (30% suspension) of 500 mPa.s (= 500 cp); and d) maximum viscosity in diethylenglycol polyadipate (30% suspension) of 35.000 mPa.s (= 35.000 cp).

Inventors: MANS FIBLA VICENTE, TORAL DALMAU LUISA, MANS FIBLA, VICENTE, TORAL DALMAU, LUISA
Applicants: BUDENHEIM IBERICA S L SOCIEDAD, BUDENHEIM IBERICA, S.L. SOCIEDAD EN COMANDITA
Application year: 1993
Main classification: C01B25
IPC codes: C01B25