EP0425577A1 - Polyphosphonates organiques macrocycliques - Google Patents

Polyphosphonates organiques macrocycliques

Info

Publication number
EP0425577A1
EP0425577A1 EP19890909018 EP89909018A EP0425577A1 EP 0425577 A1 EP0425577 A1 EP 0425577A1 EP 19890909018 EP19890909018 EP 19890909018 EP 89909018 A EP89909018 A EP 89909018A EP 0425577 A1 EP0425577 A1 EP 0425577A1
Authority
EP
European Patent Office
Prior art keywords
macrocyclic
formula
composition according
integer
stabiliser
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19890909018
Other languages
German (de)
English (en)
Inventor
Gareth Wilmot Morris
Neil David Feasey
Paul Andrew Ferguson
Dirk Van Hemelrijk
Michel Charlot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Interox Ltd
Original Assignee
Solvay Interox Ltd
Interox Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solvay Interox Ltd, Interox Chemicals Ltd filed Critical Solvay Interox Ltd
Publication of EP0425577A1 publication Critical patent/EP0425577A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/037—Stabilisation by additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6524—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having four or more nitrogen atoms as the only ring hetero atoms

Definitions

  • the present invention relates to organic polyphosphonates and particularly to macrocyclic organic polyphosphonates, a process for the preparation of these compounds, and stabilised aqueous solutions of hydrogen peroxide.
  • the process for stabilising aqueous solutions of hydrogen peroxide using such stabilisers also comes within the scope of the invention. It is already well known particularly through the patent US-A-4001212 (E I Dupont de Nemours and Company) how to synthesise macrocyclic polyamines containing 3 to 7 atoms of nitrogen.
  • the purpose of the invention is to provide compounds derived from macrocyclic polyamine organic polyphosphonates having particular properties, thereby rendering them particularly suitable for certain purposes, and especially for stabilising peroxygen compounds.
  • the inve relates to macrocyclic organic polyphosphonates belonging to the class of macrocyclic poly (methylene phosphonic acid) polyamines having the following general formula 1:
  • n is an integer of from 2 to 5 which can remain the same or vary within the same molecule
  • m is an integer of from 3 to 7
  • Me represents an- element selected from hydrogen, an ammonium group, an alkali metal or an alkaline earth metal and x represents the valency of the element Me.
  • polyphosphonates according to formula 1 have proved to have a good capacity for stabilising hydrogen peroxide.
  • polyphosphonates in accordance with formula 1 which have proved to be particularly advantageous are those in which the element Me is chosen from alkali metals or alkaline earth metals. Alkali metals are preferred, and - most conveniently sodium.
  • the macrocyclic poly(methylene phosphonic) polyamines according to formula 1 can be obtained by reaction between macrocyclic polyamines, formaldehyde and phosphorous acid: for example, according to the reaction scheme (A) below:-
  • the operating conditions under which the catalytic synthesis of the macrocyclic polyphosphonates from the corresponding macrocyclic polyamine according to formula 1 is carried out are those which are well known for polyphosphonate preparation generally, such as described by Moedritzer and Irani; Journal of Organic Chemistry, 1966,
  • the synthesis is carried out in a reaction mixture containing strong acid, which is typically mineral acid catalyst, and especially is sulphuric acid or hydrochloric acid.
  • strong acid typically mineral acid catalyst, and especially is sulphuric acid or hydrochloric acid.
  • a small excess such as up to 100% above the stoichiometric amounts of formaldehyde and phosphorous acid are preferred.
  • Reaction is often carried out at or within 10°C below reflux conditions, typically for 1 to 6 hours.
  • the resultant product is in the acid form and can be appropriately neutralised with suitable alkali earth bases or ammonia to produce the corresponding salts.
  • the present inventio relates to an aqueous solution of hydrogen peroxide containi an effective amount of a stabiliser selected from macrocycli organic polyphosphonates having the general formula 1:
  • Aqueous solution of hydrogen peroxide means any aqueous solution of hydrogen peroxide whose concentration by weight is between 0.1 and 99g H 2 0 100g of solution and preferablybetween 0.5 and 95g H 2 O 2 /100g of solution.
  • this solution can be a commercial solution of hydrogen peroxide with a concentration by weight of between 25 and 70g H O /100g of solution, or more dilute solutions sold for some purposes containing from 2.5 to 12.5g H 2 O 2 /100g solution.
  • the most highly desirable macrocyclic organic polyposphonate content of the aqueous solution of hydrogen peroxide according to the invention depends on various parameters, including, particularly, the concentration of the hydrogen peroxide solution, its pH and the nature of the polyphosphonate selected, particularly its parameters n and m and the element Me, and also the nature of the end-use of the solution.
  • a further factor influencing the stabiliser concentration, to some extent interrelated to the end use, comprises the extent and type of contaminants likely to be encountered by. the aqueous hydrogen peroxide solution, and particularly transition metal ions such as iron or copper.
  • transition metal ions such as iron or copper.
  • the aqueous solution of hydrogen peroxide contain at least 0.5mg macrocyclic organic polyphosphonate or salt thereof per kg of solution, and preferably not more than 1500mg.
  • the preferred contents are between 1 and 1000mg and amount chosen will usually take into account the above-identified parameters and factors.
  • the invention has equal applicability to solutions of hydrogen peroxide which are acid, neutral or basic, such as from pHO to pH14. In particular, it finds an advantageous application for all acid solutions whose apparent pH is between 0 and 5, and the aqueous solutions used for the electronics industry, which have to be very pure can be highlighted.
  • solutions suitable for stabilisation in accordance with the instant invention are the solutions of hydrogen peroxide used for cleaning optical glass, particularly contact lenses, solutions of H 2 0 2 for hydrometallurgy, particularly the extraction of metals by leaching of ores or in the selective recovery of metals, H 2 0 2 solutions for engraving, pickling and polishing metals (for example liquors for the chemical polishing of copper, such as those described in patent application FR-A-87.13407 (Solvay and Co), H 0 2 solutions used for the protection of the environment, such as those used for detoxifying liquid or gaseous effluent and those used for the purification or disinfection of water, solutions of H 2 0 used in the food industry and, in particular those used for the disinfection of packaging and containers.
  • the aqueous solution of hydrogen peroxide can be an aqueous bleaching liquor containing hydrogen peroxide in a concentration of between 0.5 and 50g H O 2 /100g of solution.
  • bleaching liquors which are basic in nature, are the washing or bleaching liquors containing hydrogen peroxide for textile materials and the bleaching liquors containing hydrogen peroxide for pulps.
  • the invention also relates to a process for stabilisin a peroxygen compound in which the compound is brought into contact with an effective amount of a stabiliser containing one or more phosphonate groups, characterised in that the stabiliser belongs to the class of macrocyclic poly ( ethylene phosphonic) organic polyphosphonates having the following general formula 1:
  • n is a whole number between 2 and 5 and m is also a whole number between 3 and 7
  • Me represents an element selected from hydrogen, the ammonium group, alkali metals and alkaline earth metals x means the valency of the element Me.
  • peroxygen compound indicates herein a compound containing essentially the part structure -0-0- .
  • the stabilising process' is particulary suitable for stabilising solutions of peroxygen compounds, such as an aqueous solution of hydrogen peroxide, by directly incorporating th stabiliser in the solution.
  • the stabiliser is typically applied to the surface of the peroxygen compound, often in solution an remains on the surface or impregnates into the solid.
  • the stabiliser can be present during the crystallisation of the peroxygen compound and thereby incorporated throughout the solid during manufacture.
  • the invention has the advantage of providing aqueous solutions of hydrogen peroxide whose stability is improved with regard to decomposition brought about by the cations o heavy metals and transition metals in comparison with the known and commercially available organic stabilisers based upon organic -phosphonates.
  • the non-limiting examples that follow are given with a view to illustrating the invention. Those not in accordance with the invention bear the suffix R.
  • Example 1 This Example illustrates the preparation of the macrocyclic polyphosphonates according to the invention.
  • the flask fitted with a reflux condenser, was placed a thermostat and heated to 120°C. 2ml of an aqueous solution of formaldehyde containing 37% by weight formaldehyde was then added drop wise in a continuous manner over a period of one hour.
  • the reaction mixture was kept at 120°C for two hours and then permitted to cool to ambient temperature.
  • the final product was a yellow liquid.
  • the NMR analysis of thi liquid shows that 82% of the phosphorus is in the form of methylene phosphonate.
  • the product obtained is 1,4,7,10,13,16-Hexaazacyclo-octadecane hexa (methylene phosphonic) acid, also known as hexacyclenemethylenephosphonate or HCMP. Examples 2R to 7.
  • a test mixture wit a concentration of 40.2g H 2 O 2 /100g solution and containing 2.28 ppm metals and a stabiliser in a stabiliserrmetals molar ratio equal to 1.0 was thus obtained.
  • the pH of the final mixture was then adjusted to 2.5 using a small quantity of HCl or concentrated NaOH, as necessary.
  • test tube A 25ml sample of the test mixture was then removed and introduced into a 50ml test tube with a ground glass neck. After the ground glass of the tube had been greased with silicone grease, the tube was assembled with a water manometer. The test tube and the manometer together were then immersed in a thermostat adjusted to 40°C for one hour in order to bring the temperature of the whole assembly into equilibrium. The initial level was then measured with the manometer and the measurement was repeated after a residence time of 1 hour at 40°C.
  • Example 7 with the stabiliser HCMP which is in accordance with the invention gives the lowest measurement of all the stabilisers tested, thereby demonstrating that HCMP is more effective than all the commercially available stabilisers at stabilising aqueous solutions of hydrogen peroxide under otherwise identical test conditions.
  • Example 8R to 10
  • This Example illustrates the preparation of a second macrocyclic polyphosphonate according to formula 1, and specifically a derivative of cyclame.
  • cyclame 2.0g, 0.01m
  • phosphorous acid 3.28g, 0.04m
  • demineralised water 10mls
  • hydrochloric acid 10mls, 36% w/w solution
  • the mixture was heated to reflux temperature about 107°C, and formaldehyde (6.01mls, 37% w/w solution, 0.08m) introduced gradually over a period of an hour whilst maintaining reflux conditions, which were subsequently maintained for a further hour.
  • an aqueous solution of 85% by weight H 2 0 2 was diluted with twice distilled water to form an aqueous solution of 70% byweight H 2 0 2 in a 100ml beaker pas ⁇ ivated in the manner described above.
  • a contaminating solution containing FeCl3.6H 2 0 was then added in order to obtain a concentration therein of 3.45.10 "* ⁇ g Fe ⁇ + /litre and 7.85.10 ⁇ Cu + g/1. 1000mg of stabiliser used per kg of aqueous solution of 70% by weight H 2 0 2 were then added.
  • the solution was then diluted with its own volume of twice distilled water, and had a pH of 2.42.
  • the stabilisers tested were 1,5,8,12- tetraazacyclotetradecanetetra (methylene phosphonic) acid, cyclame methylene phosphonate (CMP) produced in accordance with Example 11 of the invention, in Example 13, and a stabiliser D2010 not in accordance with the invention in Example 12R which was the fully acid form of D2016 previously mentioned herein.
  • the volume of oxygen liberated over a period of three hours at 40°C was measured by the same type of apparatus as described for Examples 2R to 10, and used to calculate a gassing rate for each Example. These were 0.027mls 0 2 /min in Example 12R and 0.009mls 0 2 /min in Example 13.
  • CMP cyclame methylene phosphonate
  • Example 14 In this Example, a long term storage trial was conducted of a concentrated aqueous solution of hydrogen peroxide containing as stabiliser a macrocyclic polyphosphonate produced by the process described in Example 1.
  • Hydrogen peroxide solution 85% w/w was diluted with twice distilled water to 70% w/w concentration in a 500 ml erlenmeyer flask, dosed with 200 ppm HCMP, calculated as the active material, and stored at laboratory ambient temperature.
  • the residual concentration of hydrogen peroxide was measured by the standard iodide test after 6 months storage, and was found still to be 70% w/w, which indicates that the stabiliser is remarkably effective.
  • the degradation of the phosphonate itself was monitored by a technique in which the phosphorous content of two samples of the aqueous 70% w/w solution were compared. The first sample was tested straightaway and the second sample after it had been passed through active carbon in order to retain the organic phosphonates.
  • Example 15 and Comparisons 16R to 21R In this Example and comparisons, solutions of hydrogen peroxide, works 70% w/w concentration, each containing a different stabiliser, were made up in passivated beakers. The concentration of stabiliser was always 100 ppm and the pH of the solution was adjusted to an initial pH of 1.0. A 50 ml sample of each-solution was introduced into a 50 ml cylindrical vessel fitted with a silicone greased ground joint to a manometer.
  • DTPA is diethylenetriamine- pentaacetic acid.
  • Ionol and PHBN are known to trap radicals, PHBN being phenyl N-tertiary butyl nitrone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)

Abstract

L'invention concerne des polyphosphonates organiques macrocycliques appartenant à la classe des polyamines poly(méthylène phosphonique) macrocycliques ayant la formule générale (I), dans laquelle n représente un nombre entier compris entre 2 et 5 et m représente un nombre entier compris entre 3 et 7. Me représente un élément choisi parmi l'hydrogène, un groupe ammonium, un métal alcalin ou un métal alcalino-terreux, et x représente la valence de l'élément Me. Ces produits trouvent une application dans la stabilisation de solutions aqueuses de peroxyde d'hydrogène.
EP19890909018 1988-07-19 1989-07-18 Polyphosphonates organiques macrocycliques Withdrawn EP0425577A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB888817185A GB8817185D0 (en) 1988-07-19 1988-07-19 Organic polyphosphonates
GB8817185 1988-07-19

Publications (1)

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EP0425577A1 true EP0425577A1 (fr) 1991-05-08

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EP19890909018 Withdrawn EP0425577A1 (fr) 1988-07-19 1989-07-18 Polyphosphonates organiques macrocycliques

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EP (1) EP0425577A1 (fr)
GB (1) GB8817185D0 (fr)
WO (1) WO1990001034A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5714604A (en) * 1993-05-06 1998-02-03 The Dow Chemical Company Process for the preparation of azamacrocyclic or acyclic aminophosphonate ester derivatives
FR2707896B1 (fr) † 1993-07-22 1995-09-01 Chemoxal Sa Procédé de traitement d'un article et nouvelle solution aqueuse de peroxyde d'hydrogène.

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Publication number Priority date Publication date Assignee Title
US4304762A (en) * 1978-09-27 1981-12-08 Lever Brothers Company Stabilization of hydrogen peroxide
JPS61226751A (ja) * 1985-03-30 1986-10-08 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料用処理液及びその処理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9001034A1 *

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Publication number Publication date
WO1990001034A1 (fr) 1990-02-08
GB8817185D0 (en) 1988-08-24

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