WO2018233797A1 - MOLECULE FOR THE TREATMENT OF SWIMMING POOL WATER TO REMOVE ISOCYANURIC ACID - Google Patents

Abstract

The invention relates to a molecule for the treatment of swimming pool water rapidly in a few hours in order to eliminate, according to a complexation process, the isocyanuric acid contained, in order to delay (or even avoid) the emptying of the pool , characterized by a graft constituted in its composition by: - The 2,6-diaminopyridine part of the Hamilton molecule, - A natural cellulose-type polymer.

Description

 MOLECULE FOR THE TREATMENT OF SWIMMING POOL WATER TO ELIMINATE

 ISOCYANURIC ACID

DESCRIPTION

 The invention relates to a molecule for the treatment of swimming pool water rapidly in a few hours in order to eliminate, according to a complexation process, the isocyanuric acid contained, in order to delay (or even avoid) the emptying of the pool , characterized by a graft constituted in its composition by:

 The 2,6 diaminopyridine part of the Hamilton molecule,

 A natural polymer of cellulose type.

State of knowing:

The pools undergo disinfection of the water by introducing trichloroisocyanuric acid which release hypochlorous acid and isocyanuric acid, commonly called stabilizer. The stabilizer accumulates in the basin, there is no way to eliminate it. It is therefore necessary to drain all or part of the basin.

 On the other hand, a known molecule known as "Hamilton receptor" is composed of two diaminopyridine molecules and a benzyledione molecule. This molecule is used in the complexation domains of barbiturates and merocyanines, as well as for the synthesis of supramolecular polymers by reaction with cyanuric acid and other molecules not concerned by the present invention. These fields of industrial application were previously mainly the purification of metals.

A first French patent application registered under No. 1501686, and filed by the present inventor, had established a molecular complex using the "Hamilton receptor" molecule intended to be used for the complexation of isocyanuric acid for the purpose of treating the pool waters and delay by this treatment draining the basin. This modified "hilton" receptor complex was composed of two subsets of:

 - diaminopyridines (A) positioned at the end of the chain because they are intended to trap the isocyanuric acid (C).

a functional chemical group (B) positioned in the middle of the chain on the benzyldone portion to hold the Hamilton receptors on a solid support. This functional group is characterized in that it is attached to the Hamilton receptor on the benzene nucleus (D) without obscuring the perimeter of said receptor so that the latter retains its field of action and without causing steric hindrance. According to this patent, the process for removing isocyanuric acid (C) consisted of a complexing action of isocyanuric acid by the Hamilton receptor. This is characterized by 6 hydrogen bonds (H) between the oxygen atoms (O) of isocyanuric acid (C) and the hydrogens (H) of the primary and secondary amino functions of the Hamilton receptor, and with the Nitrogen atoms (N) of the Hamilton receptor and the hydrogens (H) of the secondary amino functions of isocyanuric acid (C).

 However, the difficulty encountered in industrializing this complexation was that no anchor point attached to the functional chemical group (B) allowed the complex to be grafted onto a solid support, because of the steric hindrance caused by the support coming from counteract the action of the molecular complexion, so that the practical use of the invention in pond water was made impossible because of the attachment to the unsolved support. It is to overcome this uncertainty that the present invention is dedicated.

Presentation of the invention

 The invention relates to a molecule intended for the treatment of pool water in a few hours in order to eliminate, according to a complexing process, the isocyanuric acid contained in order to delay (or even avoid) the emptying of the pool, a molecule characterized by a graft constituted in its composition by:

 The 2,6-diaminopyridine part of the Hamilton molecule,

 A natural polymer of cellulose type.

 Between 10 and 30% of the polymers hold the 2,6-diaminopyridine portion of the Hamilton molecule.

 In addition, the cellulose-type natural polymer which makes the action of the molecule optimal, is of the alpha cellulose type.

 The manufacturing process of the molecule is characterized by two successive stages of:

 Step 1: modification of the cellulose-based solid support comprising oxidation in an aqueous medium using sodium bromide, sodium hypochlorite, and in the presence of an oxoammonium salt,

 Step 2: synthesis of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose comprising a grafting of the solid support with 2,6-diaminopyridine, by means of coupling agents, preferentially the EDC / NHS pair.

For use in swimming pool water, the complexation is carried out by adding to a pool water concentrated in isocyanuric acid between 100 and 250 mg / L, a complexing concentration of between 50 mg / L and 4 g / L for a minimum of one hour. In the manufacturing phase, the first step of modifying the solid support is characterized by a series of successive operations consisting of:

 An oxidation in a reaction medium where the temperature is maintained at 4 ° C. during the addition of the products as well as for the entire reaction time,

 an oxidation carried out in a reaction medium whose pH is initially between 10 and 12 and is stabilized at pH 10 during the duration of the reaction,

 the addition of sodium hypochlorite under control so as not to disturb the pH of the reaction medium too much,

 an oxidation which ends when the pH of the reaction medium no longer changes, preferably after 24 hours of reaction,

 a reaction that is stopped by adding an excess of primary alcohol,

 the introduction of the solid support, recovered in the reaction medium after reaction, in an acidification medium, preferably one or more 2.5M hydrochloric acid solutions, for a period of 30 to 90 minutes and then in distilled water for a period of duration of 90 minutes,

 at the end of the reaction and washing, the solid support has an oxidation state greater than 30%.

The second manufacturing step is the synthesis of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose comprising a grafting of the solid support with 2,6-diaminopyridine, by means of coupling agents, preferably the EDC couple. NHS, is characterized by a series of successive operations consisting of:

 a grafting carried out in a reaction medium whose pH is initially between

7 and 8,

 a reaction carried out in a reaction medium where the temperature is maintained at

4 ° C during the addition of the coupling agents,

 a stopped reaction, preferably after 24 hours of reaction, by adding an acid to reduce the pH to 1-2,

 washing with a soxhlet of acetone in order to remove the 2,6-diaminopyridine still present in free form in the modified cellulose,

 at the end of the reaction and washing, the modified cellulose has between 10% and 30% of grafted units,

 - Grafting rate of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose determined using Elemental Analysis.

In use, the complexation is carried out by adding to a pool water concentrated in isocyanuric acid between 100 and 250 mg / L of a complexing concentration of between 50 mg / L and 4 g / L for a period of one hour minimum.

Claims

 1. Molecule intended for the treatment of swimming pool water in a few hours with the aim of eliminating the isocyanuric acid contained in the purposes of a complexing process, to delay - or even to avoid emptying the pool, a molecule characterized by a graft constituted in its composition by:  The 2,6-diaminopyridine part of the Hamilton molecule,  A natural polymer of cellulose type.  -2, pool water treatment molecule according to claim 1, characterized in that between 10 and 30% of the polymers hold the 2,6 diaminopyridine portion of the Hamilton molecule. 3. Swimming pool water treatment molecule according to claim 1 characterized in that the cellulose-type natural polymer is alpha cellulose type, making the action of the molecule optimal.  4. Process for the manufacture of the molecule according to claim 1, characterized by two successive stages of:  Step 1: modification of the cellulose-based solid support comprising oxidation in an aqueous medium using sodium bromide, sodium hypochlorite, and in the presence of an oxoammonium salt,  Step 2: synthesis of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose comprising a grafting of the solid support with 2,6-diaminopyridine, by means of coupling agents, preferentially the EDC / NHS pair, 5. Pool water treatment molecule according to claim 1, characterized in that in use, the complexation is carried out by adding to a pool water isocyanuric acid concentrated, between 100 and 250 mg / L, a complexing concentration of between 50 mg / l and 4 g / l for a minimum of one hour. 6. The manufacturing method according to claim 4 in that the modification of the solid support is characterized by a series of successive operations consisting of:  an oxidation in a reaction medium where the temperature is maintained at 4 ° C. during the addition of the products as well as for the entire reaction time.  an oxidation carried out in a reaction medium whose pH is initially between 10 and 12 and is stabilized at pH 10 for the duration of the reaction.  the addition of sodium hypochlorite which is the subject of a control so as not to disturb the pH of the reaction medium too much.  an oxidation which ends when the pH of the reaction medium no longer changes, preferably after 24 hours of reaction. a reaction that is stopped by adding an excess of primary alcohol. the introduction of the solid support, recovered in the reaction medium after reaction, in an acidification medium, preferably one or more 2.5M hydrochloric acid solutions, for a period of 30 to 90 minutes and then in distilled water for a period of duration of 90 minutes,  at the end of the reaction and washing, the solid support has an oxidation state greater than 30%. 7. The manufacturing method according to claim 4 in that the synthesis of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose comprising a grafting of the solid support with 2,6-diaminopyridine, by means of coupling agents. , preferentially the EDC / NHS pair, is characterized by a series of successive operations consisting of:  a grafting carried out in a reaction medium whose pH is initially between 7 and 8,  a reaction carried out in a reaction medium where the temperature is maintained at 4 ° C. during the addition of the coupling agents,  a stopped reaction, preferably after 24 hours of reaction, by adding an acid to reduce the pH to 1-2,  washing with a soxhlet of acetone in order to remove the 2,6-diaminopyridine still present in free form in the modified cellulose,  At the end of the reaction and washing, the modified cellulose has between 10% and 30% of grafted units,  The degree of grafting of (2-amino-6-pyridinecarboxamidyl) -6-deoxycellulose determined using Elemental Analysis.