NO842459L - NEW COMPOUNDS CONTAINING QUARTERLY AMMONIUM AND METHYLENE PHOSPHONIC ACID GROUPS AND THEIR USE FOR AA HOME CREATION OF THE GEMSTONE. - Google Patents

Description

The use of methylenephosphonic acid-substituted alkylene polyamines for metal ion regulation at less than stoichiometric amounts was suggested in a patent belonging to Bersworth (US Patent 2,609,390) in 1952. Later, a water-dispersible polymeric amine chelating agent, which included alkylene phosphonate derivatives, stated to have "threshold effects in gallstone inhibition applications (see US patent 3,331,773), this term being used to describe the use of the agent in less than stoichiometric quantities. Diamine and polyamine methylene phosphonate -derivatives are described and claimed in US patents 3,336,221 and 3,434,969, respectively. Some of the products described in these two patents are available commercially and are recommended as scale inhibitors when used in threshold amounts .

Some other patents that describe heterocyclic nitrogen-containing compounds that are suitable as chelating agents and can be used in threshold amounts are US Patents 3,674,804, 3,720,498, 3,743,603, 3,859,211, and 3,954,761.

Methylene phosphonates of polyalkylene polyamines, described in US patent 4,051,110, are prepared by reacting di- or polyamines with a chain-extending agent such as a di-halide or an epoxy halide, for example ethylene dichloride or epichlorohydrin, and then with phosphoric acid and formaldehyde . Thus, for example, triethylene tetramine is reacted with epichlorohydrin in a molar ratio of approx. 1:1; then the product is reacted with phosphoric acid and formaldehyde in the presence of hydrochloric acid. The resulting methylenephosphonated polyamine is suitable in small quantities as a scale inhibitor, being used in concentrations of 20-50 ppm.

Certain phosphonic acid derivatives of the aliphatic acids can be prepared by reacting phosphoric acid with acid anhydrides or acid chlorides, for example the anhydrides or chlorides of acetic, propionic and valeric acid. The compounds produced have the formula

where R is a lower alkyl radical with 1-5 carbon atoms. The procedure for the manufacture and use of these products is described in US patent 3 214 4 54. The use of

threshold amounts for preventing calcium precipitation are described and a patent applied for therein.

Compounds such as the product of the reaction between a halogen hydride, for example epichlorohydrin, and an amine, for example trimethylamine, give quaternary ammonium chlorohydrin adducts, which have biological activity. The chlorine in the chlorohydrin group can of course be further reacted with a new amine to obtain a quaternary hydroxyalkylammonium compound and adduct of the amine.

It has now been discovered that such a functionality will, when attached to a diamine or polyamine which also contains a methylene-phosphonic acid group, give a compound with improved threshold activity, i.e. it inhibits the precipitation of metal ions from solution at less than stoichiometric amounts.

Briefly, the invention comprises compounds with improved properties in connection with inhibition of the precipitation of metal ions when used in threshold quantities, and such have been made which are derivatives of ammonia or di-

or polyamines where the amine hydrogen atoms have been substituted with both methylenephosphonic acid groups or their salts and 2-hydroxy-3-(trialkylammonium halide)propyl groups. These compounds have the formula

where the substituents A, B, C and D are each independently selected from hydrogen; methylenephosphonic acid or salts thereof; 2-hydroxy-3-(trialkylammonium halide)propyl wherein each alkyl group contains 1-5 carbon atoms; a group with the formula

where R is an unsubstituted or inert substituted alkyl group with 1-6, preferably 1-3, more preferably 1 carbon atoms, or salts thereof; n is 0-15, and where said substituents include at least one methylenephosphonic acid group or salt thereof and at least one 2-hydroxy-3-(trialkylammonium halide)-propyl group.

Reactants used for the production of the products according to the invention are ammonia, alkylene amines, polymeric amines and polyethylene imines with different molecular weights, so

such as those obtained from the Cordova Chemical Company. Various metal and alkali metal salts, ammonium and amine salts and partial salts of the methylenephosphonic acids and mixtures thereof can be used for the preparation of the quaternized derivatives according to the invention. However, it must be noted that the quaternization of the amine should preferably precede the phosphonomethylation and the preparation of any of the methylenephosphonic acid salts.

Almost all amines containing reactive amine hydrogen atoms can be used for the production of the products. Thus, for example, polyglycolamines, amidoamines, oxyalkylated amines, carboxymethylated amines, methylene-sulfonated and hydroxypropyl-sulfonated amines, nitrogen heterocyclic compounds and the like can be used as reactant. The preferred products are those where the amine hydrogen atoms have been completely replaced, although some unreacted amine hydrogen atoms may remain.

The following examples are representative of the preparation of the compounds according to the invention and of the preparation of the fully phosphonated compounds for comparison.

EXAMPLE 1

Ethylenediamine (EDA) (15 g, 0.25 mol) and 94 g (0.25 mol)

of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride was placed in a 500 ml round-necked reaction flask equipped with a water-cooled reflux condenser, mechanical stirrer, thermometer with temperature regulator and an addition funnel. The reaction mixture was heated to 90°C and digested for approx. 1 hour and cooled. About. 60 g of concentrated hydrochloric acid solution and 67.5 g (0.82 mol) of phosphoric acid were added to the reaction flask and heated to reflux and kept at this for 1 hour. Aqueous 37% formaldehyde solution (67.4 g, 0.83 mol) was weighed into the addition funnel and added over a period of 2 hours. The reaction mixture was heated at reflux for an additional 3

hours and then cooled. The product was the derivative of EDA where one hydrogen atom had been replaced by 2-hydroxypropyltrimethylammonium chloride groups and the remaining hydrogen

atoms with methylenephosphonic acid groups.

EXAMPLE 2 (Comparison example)

Ethyleneamine E-100x (12.5 g) and 12.5 g of deionized water

was placed in a 500 ml round-bottomed reaction flask equipped as described in example 1. Approx. 110 g of concentrated hydrochloric acid solution and 31.1 g (0.38 mol) of phosphoric acid were added to the reaction flask and heated to reflux and kept at this for 1 hour. Aqueous 37% formaldehyde solution (26.8 g, 0.33 mol) was weighed into the addition funnel and added over a period of 1 hour. The reaction mixture was heated at reflux for an additional 3 hours and then cooled. The product was the derivative of E-100 where all the amine hydrogen atoms had been replaced with methylenephosphonic acid groups.

EXAMPLE 3

Ethyleneamine E-100 (12.5 g) and 12.5 g of deionized water

was placed in a 500 ml round-necked reaction flask as in example 2 and heated to 90°C. A 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium chloride (12.0 g, 0.032 mol) was weighed into the addition funnel and added over a period of 10 minutes. The reaction mixture was heated for an additional 1 hour at 90°C and cooled. About.

110 g of concentrated hydrochloric acid solution and 28.5 g (0.35 mol) of phosphoric acid were added to the reaction flask and heated to reflux and kept at this for 1 hour. Aqueous 37% formaldehyde solution (24.5 g, 0.30 mol) was weighed into the addition funnel and added over a period of 1 hour. The reaction mixture was heated at reflux for an additional 3 hours and then cooled. The product was the E-100 derivative where -10% of the amine hydrogen atoms had been replaced with hydroxypropyltrimethylammonium chloride groups, the rest having been replaced with methylenephosphonic acid groups.

EXAMPLE 4 (Comparison example)

An aqueous polymeric polyalkylene polyamine (PAPA) solution (66.4 g 36% strength), prepared from ethyleneamine E-100 and ethylene-

<X>Ethyleneamine E-100 is a product of The Dow Chemical Company and is described as a mixture of pentaethylenehexamine plus heavier ethyleneamines with an average molecular weight of 250-300.

dichloride, was placed in a 500 ml round-necked reaction flask equipped as in example 1. Approx. 40 g of concentrated hydrochloric acid solution and 49.3 g (0.60 mol) of phosphoric acid were added to the reaction flask and heated to reflux and kept at this for 1 hour. Aqueous 37% formaldehyde solution (51.1 g, 0.63 mol) was weighed into the addition funnel and added over a period of 1 hour. The reaction mixture was heated at reflux for an additional 1.5 hours and cooled. The product was the PAPA where all the amine hydrogen atoms were

have been replaced with methylenephosphonic acid groups.

EXAMPLE 5

The polymeric polyalkylene polyamine used in Example 4 was modified by reacting 10 mol% of the available amine hydrogen atoms with 3-chloro-2-hydroxy-propyl-trimethylammonium chloride in a similar manner as described in Example 3. The resulting reaction product was then phosphonomethylated with phosphoric acid and formaldehyde in the presence of hydrochloric acid. The product was that PAPA in which ~10% of the amine hydrogen atoms had been replaced with hydroxypropyltrimethylammonium chloride groups, the remainder being replaced with methylenephosphonic acid groups.

The products according to examples 1-5 were assessed accordingly

for the following scale inhibition test with respect to calcium carbonate: Several 50 ml samples of a 0.02M CaC^ solution are placed in 120 ml bottles. The relevant inhibitor is added to these solutions in different concentrations. Samples (50 ml each) of a solution of 0.04 M sodium bicarbonate and 0.96 M sodium chloride are then added with stirring. A determination of total hardness is made for the mixture by adding an excess of standard EDTA

to a sample and back titrate with standard Mg<++-> solution in the presence of the indicator Eriochrome Black T. The samples are placed in an oven at 80°C, and 10 ml samples are withdrawn periodically from each bottle, filtered through a filter with pore diameters on

4-5.5 µm, and the total hardness of the filtrates is determined by titration. A blank test without inhibitor is run in an identical manner.

The relative inhibition effects are shown by determining the amount of hardness (as soluble calcium) before and after heating for a period of 24 hours. The amount of soluble calcium as a percentage of what was originally present is given as percent inhibition.

Results of these tests are shown in Table I and compared to the phosphonated but non-quaternized amine. All product and comparison trials were performed using a concentration of 10 ppm based on active acid.

From the above tests, it can easily be seen that the methylenephosphonic acid derivatives containing at least one quaternary group are at least as good or better than the compounds containing only the methylenephosphonic acid group, including the derivative of EDA which is indicated as a commercially available scale inhibitor -connection. It must be clear that such compounds containing only the quaternary groups do not exhibit any threshold effect and that the methylenephosphonic acid group or its salt must be present for the effect to be achieved.

While all the examples show the use of the chloride form of the quaternary group, other halides, for example Br or I, can be used as the quaternized derivative. Thus, the quaternary salt can be hydroxypropyltriethylammonium bromide, hydroxypropyltripropylammonium iodide and the like.

Claims (9)

1. Compounds with the formula where (a) n is 0-15, (b) A, B, C and D are each independently selected from among (i) hydrogen, (ii) methylenephosphonic acid and salts thereof, (iii) 2-hydroxy-3(trialkylammonium halide)propyl groups where each alkyl group has 1-5 carbon atoms, and (iv) a group with the formula where R is an unsubstituted or inert substituted alkyl group with 1-6 carbon atoms or" salts thereof, so that at least one of A, B, C and D is (ii) and at least one is (iii) . 2. Compound according to claim 1, where n is 0 or 1 and one of A, B, C or D is (iii) and the rest of the substituents are (ii) • 3. Compound according to claim 1, where n is 0. 4. Compound according to claim 2 or 3, where (ii) is present in the form of a salt of the acid. 5. Method for inhibiting scale formation in an aqueous solution containing alkaline earth metal ions, which comprises adding to said aqueous solution a threshold amount of a compound with the formula where (a) n is 0-15, (b) A, B, C and D are each independently selected from among (i) hydrogen, (ii) methylenephosphonic acid and salts thereof, (iii) 2-hydroxy-3(trialkylammonium halide)propyl groups where each alkyl group has 1-5 carbon atoms and (iv) a group with the formula where R is an unsubstituted or inert substituted alkyl group with 1-6 carbon atoms and salts thereof, so that at least one of A, B, C and D is (ii) and at least one is (iii). 6. Process according to claim 5, where n in the compound is 0 or 1 and one of A, B, C or D is (iii) and the rest of the substituents are (ii). 7. Method according to claim 5, where n in the compound is 0. 8. Process according to claim 6 or 7, where (ii) is present in the form of a salt of the acid. 9. Method according to claim 8, where the salt is a sodium salt.