Method of preparing polyphosphates of organic compounds

FIELD: synthesis of phosphorus-containing derivatives of organic compounds.

SUBSTANCE: invention relates to method of preparing polyphosphates of organic compounds, to mixture of polyphosphates of organic nitrogenous bases, and to use of polyphosphates and mixture of polyphosphates as fire retardants for plastics, preferably thermoplastics and, more particularly, polyamides and polyesters. Polyphosphates of organic compounds are prepared via exchangeable decomposition of mixture of phosphorus pentoxide and at least one organic nitrogenous base with a compound releasing water when decomposed under reaction conditions, the latter compound being used in such molar proportion that water would release in amount corresponding to essentially two moles of water per one mole of phosphorus pentoxide. Water-releasing compound can be compound forming, along with water, only volatile decomposition products and this compound can be selected from group including anhydrous oxalic acid, oxalic acid dehydrate, and formic acid. Exchangeable decomposition reaction is conducted at 100 to 250°C. Mixture of polyphosphates of organic nitrogenous bases is characterized by following properties: when heated to 320°C it looses less than 2% of its mass; pH value of its 10% water suspension exceeds 5 at 25°C, preferably from 5.2 to 7.7 and, more preferably, from 5.8 to 7; its solubility in water is less than 0.1 g and preferably less than 0.01 g per 100 mL water.

EFFECT: expanded synthetic possibilities.

6 cl, 5 ex

 

Polyphosphates and organic nitrogen bases such as guanidine and melamine, are becoming more important as flame retardants for plastics and textiles. The decomposition temperature of the mixtures of polyphosphates used as flame retardants for plastics, should be as close as possible to this indicator, the latter, as in the case of lower temperature of decomposition (decay) is already in the process of making a mixture of plastic and flame retardant can begin decomposition, leading thereby to the formation of water vapor and undesirable appearance of bubbles in the resulting plastic product. To avoid these undesirable low temperature decomposition of the flame retardant should completely exclude the presence of polyphosphate mixtures orthophosphate, and under certain conditions, and the presence of pyrophosphate.

Today, there are various ways of getting polyphosphates organic bases, however, all of these known methods has certain obvious disadvantages.

One of these ways to get organic polyphosphates reason is that first get the orthophosphate organic base and then the orthophosphate by heating to temperatures above 300°With transform in the corresponding polyphosphate organic basis of the Oia. This method is described in particular in application WO 97/44377. Required to implement a relatively high temperature make this unprofitable way, if we consider in addition the need to use the flame retardants that are the products of mass production. According to patent US 6114421 certain organic nitrogenous base is subjected in certain concentrations and under certain reaction conditions, the interaction with the anhydride of phosphoric acid.

Another known method is that conventional, commercially available polyphosphoric acid is neutralized with an organic base. However, such commercially available polyphosphoric acid is a mixture containing ortho - and polyphosphoric acid, resulting in mixtures of the products of undesired ortho - and pyrophosphate. In addition, commercially available polyphosphoric acid have a consistency from a plastic to a solid, and therefore their processing is associated with considerable difficulties. Present ortho - and pyrophosphates can turn into polyphosphates only at temperatures above 306°that is the same absolute disadvantage, as the lack of the above-described first method.

According to the third method in the source material, use of an alkali metal polyphosphate is whether the pyrophosphate of an alkali metal, which is dissolved in water and acidified with HCl. To remove chloride ions products have always wash and dry, which increases the way and requires special care in its implementation. When used as flame retardants the presence of chloride ions should be avoided, since they can lead to the formation of harmful by-products.

Based on the foregoing, the present invention was used to develop without inherent in the prior art disadvantages of simple and economical method of producing organic polyphosphates grounds provided with this extremely possible lack of products orthophosphate, and under certain conditions, and pyrophosphates.

Proposed in the invention to solve this problem the method is that the mixture of phosphorus pentoxide and at least one organic nitrogenous base is subjected to interaction with at least one connection, giving in terms of the decomposition reaction of water in such a molar ratio, at which the decomposition of this giving water connection per mole of phosphorus pentoxide is formed mainly of a maximum of 2 mol of water. Obtained according to the invention polyphosphates are condensed phosphates with chain length, as well is at least 2.

Thus unexpectedly been successfully overcome inherent in the prior art problem associated with homogeneous and uniform distribution of the required amount of water in the mixture of phosphorus pentoxide and grounds. The required amount of water is distributed normally pre-loaded with a mixture of phosphorus pentoxide and an organic nitrogenous base is absolutely homogeneous and uniformly, thus avoiding the presence in such cases, excess water, which leads to the formation of ortho - and pyrophosphoric acid.

Put the basis of the invention the task regardless of the specific conditions of implementation of its proposed method can be solved by a mixture of polyphosphates, organic nitrogenous bases that (a) when heated to 320°lose less than 2 wt.% their number, b) have a pH value of 10 wt.%-Noah aqueous suspension at 25°With more than 5, preferably from 5.2 to 7.7, especially from about 5.8 to 7.0, and C) have a solubility in water at 25°With less than 0.1, preferably less than 0.01 g per 100 ml of water.

Such a mixture of polyphosphates it is expedient to obtain the above described method according to the invention.

As giver of the water of acceptable compounds are in principle all compounds which in appropriate circumstances, the exchange reactions are decomposed with the formation of water, such as containing cristallization water substances borax, aluminum hydroxide or magnesium hydroxide, which, however, can be used only if the decomposition products of these compounds in mixtures of polyphosphates do not have any negative effects when using the last or even provide certain advantages. It is preferable to use as the water returning such compounds, decomposition of the water formed only volatile products, preferably oxalic acid in anhydrous form or in the form of dihydrate or formic acid, or such compounds, decomposition of the water formed only of carbon dioxide and carbon monoxide, leaving due to its volatility from the reaction mixture.

The molar ratio used in the reaction mixture components in accordance with the above values should be selected so that the mole P2O5in the mixture formed a maximum of about 2 moles of water. It should be noted that the decomposition of oxalic acid (anhydrous) for each mol produces 1 mol of water, and in the case of the dihydrate of oxalic acid produces 3 mol. Upon receipt of the pyrophosphates of the original substance used in such a molar ratio that the mol P2About5formed mainly of 2 mol of water, odavamatest connection. Upon receipt of polyphosphates with long chain specified value is approximately 1 mol of water per mol of P2O5. The concept of "approximately" or "predominantly" in the context of the present description means that the actual value can typically vary in either direction from the specified value by 10%, preferably 5%.

As organic nitrogenous bases can be used according to the invention any suitable for the purposes named from the number of known nitrogenous bases, such as polyvinyliden, polyethylenimine, piperazine, methylenediamine, melamine, guanidine, metropolin or their condensates, and mixtures thereof. Preferred are melamine and guanidine. Presumably if nitrogenous bases have some basic balance, the molar ratio between the original substances should be selected so that, when provided the corresponding pyrophosphate and full saturation coreóate the remnants to provide based on each of the P-atom in the product use mainly 2 moles of the base. When provided for receiving polyphosphates long chain used the molar ratio between the base and the R should be predominantly 1:1 (the ratio between the base and R2About5mainly should sostav the RT 2:1). Through the appropriate choice of the molar ratio degree of saturation of the core residues may vary.

The exchange reaction according to the invention can be carried out at ambient temperature, however, from a practical point of view it flows too slowly, it is therefore to carry out the reaction at elevated temperature, especially in the range from 100 to 250°C, preferably from 180 to 250°and most preferably from 200 to 220°C. the Preferred minimum temperature equal to 200°exceeds the melting temperature of oxalic acid, which has a positive effect on the reaction components together. However, used a temperature substantially below the temperature required for the implementation of the known methods, i.e. exceeding 300°C. This factor ensures efficiency of the proposed method, taking into account that due to the homogeneous distribution of water in the reaction mixture it is possible to avoid the formation of orthophosphate and under certain conditions pyrophosphate.

In the preferred embodiment proposed in the invention method, first the required amount of phosphorus pentoxide is mixed with an organic nitrogenous base, the mixture is then heated to a prescribed temperature, then add necessary if estvo giving water connection and by mixing homogeneous distributed in the reaction mixture.

Proposed in the invention a mixture of polyphosphates can be successfully used as flame retardants for plastics, preferably thermoplastics, especially polyamides and polyesters.

Below the invention is explained in more detail with examples of its implementation.

Example 1

In the heated liquid fuel kneading machine with two Z-shaped kneading bodies and a useful volume of 5 l load 1250 grams (10 moles) of melamine and 710 g (5 moles) of phosphorus pentoxide. The mixture is homogenized and heated to a temperature of 220°C. and Then for 15 min add 450 g (5 moles) of anhydrous oxalic acid and stirred. Upon completion of the process of adding and mixing the reaction continued for another 15 min, and then kneading machine unload formed melaminoformal.

Example 2

In the kneading machine described in example 1 type mix 1260 g (10 moles) of melamine and 710 g (5 moles) of phosphorus pentoxide and heated to a temperature of 220°C. Then analogously to example 1 for 15 min add anhydrous oxalic acid, but in the amount of 900 g (10 moles). After a further 15 min reaction at 220°from kneading machine unload net domelementforpath.

Example 3

In a laboratory mixer with lemasney blades with a useful volume of 10 l and heated liquid fuel double jacket) is t 3780 g (30 moles) of melamine with 2130 g (15 moles) of phosphorus pentoxide and heated to a temperature of 200° C. and Then for 30 min add 630 grams (5 moles) of oxalic acid dihydrate. After continuing for 15 min final stage of the reaction from the mixer unload formed melaminoformal.

Example 4

In the mixer, similar to that described in example 3 is mixed 5400 g (30 moles) of guanidine carbonate with 2130 g (15 moles) of phosphorus pentoxide and heated to a temperature of 250°C. and Then for 1 h add 1350 grams (15 moles) of anhydrous oxalic acid. After continuing for 1 h in the final stage of the reaction from the mixer unload formed guanidinoacetate.

Example 5

In the kneading machine, similar to that described in examples 1 and 2, mix 861 g (10 moles) of piperazine with 710 g (5 moles) of phosphorus pentoxide and heated to a temperature of 100°C. and Then for 15 min add 210 g (1,7 mole) of oxalic acid dihydrate. After 1 hour the final stage of the reaction the formed piperazinylmethyl unload.

1. The method of obtaining polyphosphates and organic bases, in which a mixture of phosphorus pentoxide and at least one organic nitrogenous base is subjected to reaction metabolic decomposition, at least one connection, giving the decomposition under the reaction conditions of the water, in such a molar ratio, at which the decomposition of giving water connection on the mole pentoxide is phosphorus are formed, essentially, a maximum of 2 mol of water, characterized in that as giving the water connection, use the connection that forms in addition to water only volatile decomposition products, which is selected from the group comprising anhydrous oxalic acid, dihydrate of oxalic acid and formic acid, the reaction of the exchange decomposition is carried out in the temperature range from 100 to 250°C.

2. The method according to claim 1, characterized in that as organic nitrogenous bases use melamine, and/or guanidine, and/or piperazine, preferably melamine.

3. The method according to claim 1 or 2, characterized in that the exchange reaction of decomposition is carried out at a temperature of from 180 to 250°C, preferably from 200 to 220°C.

4. The use of polyphosphates obtained by the method according to one of claims 1 to 3, as flame retardants for plastics, preferably thermoplastics, especially polyamides and polyesters.

5. A mixture of polyphosphates, organic nitrogenous bases that are used as flame retardants for plastics, characterized in that it is produced by interaction of a mixture of phosphorus pentoxide and at least one organic nitrogenous base, at least one connection, giving the water decomposition under the reaction conditions, which in addition to water forms only volatile decomposition products, and entries batch is e is carried out in such a molar ratio, when in the decomposition of the specified giving water connection per mole of phosphorus pentoxide formed, essentially, a maximum of 2 mol of water, with the resulting mixture has the following properties:

a) when heated to 320°With the loss of its mass is less than 2 wt.%,

b) the pH value it 10 wt.%-Noah aqueous slurry is at 25°With more than 5, preferably from 5.2 to 7.7, especially from about 5.8 to 7.0, and

in its solubility in water at 25°C is less than 0.1, preferably less than 0.01 g per 100 ml of water.

6. The use of a mixture of polyphosphates according to claim 5 as a flame retardant for plastics, preferably thermoplastics, especially polyamides and polyesters.



 

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28 cl, 116 ex, 52 tbl

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< / BR>
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< / BR>
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< / BR>
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< / BR>
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< / BR>
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< / BR>
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< / BR>
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