WO1992006122A1 - Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene - Google Patents
Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene Download PDFInfo
- Publication number
- WO1992006122A1 WO1992006122A1 PCT/EP1991/001846 EP9101846W WO9206122A1 WO 1992006122 A1 WO1992006122 A1 WO 1992006122A1 EP 9101846 W EP9101846 W EP 9101846W WO 9206122 A1 WO9206122 A1 WO 9206122A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- organophosphonic
- solution
- polymer
- polymers
- acid
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F30/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
Definitions
- Organophosphonic polymers and their use as stabilizers in aqueous hydrogen peroxide solutions Organophosphonic polymers and their use as stabilizers in aqueous hydrogen peroxide solutions
- the present invention relates to organophosphonic polymers comprising hydroxyl groups and a process for the manufacture of such polymers.
- Organophosphonic polymers have been known for a long time.
- the phosphonic groups are carried by an unsubstituted al yl or arylalkyl chain (Anbar M., St. John GA and Scott AC "Organic Polymeric Polyphosphonates as Potential Préventive Agents of Dental Caries: In Vitro Experiments" Journal of Dental Research, 1974, 53 (4), pages 867 to 878, * pages 869 and 870 *.
- the invention overcomes this disadvantage of known products by providing a new product capable of effectively stabilizing and for long periods of concentrated hydrogen peroxide solutions against the decomposition induced by contamination of metal ions.
- the invention relates to organophosphonic polymers which correspond to the following general formula: in which Y is a methyl group, ethyl or a hydrogen atom and Z represents a hydrogen atom, the ammonium group, an alkali metal or alkaline earth metal atom.
- Y is a methyl group, ethyl or a hydrogen atom
- Z represents a hydrogen atom, the ammonium group, an alkali metal or alkaline earth metal atom.
- the products in which Y represents a methyl group or a hydrogen atom and where Z represents an alkali metal atom or the ammonium group are especially worthy of interest, in particular the poly- ⁇ - (hydroxyvinylphosphonates) of alkali metal.
- the invention also relates to a process for manufacturing said polymers according to which the following three consecutive stages are carried out:
- Y represents a hydrogen atom
- ketene proper is particularly suitable.
- Diethylphosphite is an ester of phosphorous acid which corresponds to the following structural formula: H0-P (OC2H5) 2.
- the monomer obtained in the first step of the process according to the invention is a diethyl-1-acetoxyalkenylphosphonate which corresponds to the formula:
- Y-CH C (0C0CH3) (0P (0C 2 H5) 2 )
- Y representing a hydrogen atom, the methyl group or the ethyl group.
- the catalyst used in the first step belongs to the category of acid catalysts. Any proton-donating inorganic acid or Lewis acids well known per se such as, for example, sulfuric acid, aluminum trichloride, boron trifluoride and antimony trifluoride can be used.
- the coordination complexes that Lewis acids form with ethers are also well suited to catalyze the synthesis reaction of the monomer.
- the complexes of Lewis acids with diethyl ether are particularly suitable and, in particular, boron trifluoride etherate of formula:
- the first step is carried out in the liquid phase by introducing the ketene into the diethylphosphite containing the dissolved catalyst.
- inert solvent any solvent which does not interfere with the reagents used or with the catalyst.
- solvents are aliphatic and aromatic hydrocarbons which are liquid under the reaction conditions, aliphatic ethers such as ethyl ether and chlorinated solvents such as carbon tetrachloride. Toluene is a particularly suitable solvent.
- the temperature of the first stage is not a critical variable by itself. When working at atmospheric pressure, it must be chosen in each case according to the ketene used so as to ensure good contact between the ketene and the diethylphosphite. In cases where the ketene used is in the gaseous state, it is recommended to moderate the reaction temperature to maintain sufficient solubility of the ketene in the reaction medium. It is also possible to work at pressures higher than the atmospheric pressure.
- the polymerization of the monomer obtained in the first step is preferably carried out by radical route under the atmosphere of an inert gas such as nitrogen, in solution in a solvent and in the presence of a free radical initiator of the peroxide type.
- the solvents suitable for this type of polymerization are very suitable, and in particular the aliphatic alcohols. Examples of such solvents are isobutyl and isoamyl alcohols as well as 1-pentanol. Isobutyl alcohol has been found to be particularly interesting.
- the free radical initiator can, according to the invention, be any organic peroxide used to catalyze radical type polymerizations.
- peroxides are dibenzoyl peroxide, t-butyl peroxides and peroxydicarbonates, in particular cyclohexyl and t-butyl peroxydicarbonates.
- T-butyl-peroxy-2-ethylhexanoate gave the best results.
- An interesting variant for the second stage of polymerization of the monomer consists in carrying out the polymerization in the mass without making use of a solvent.
- the duration and temperature of the monomer polymerization reaction is not critical in itself. They must be adjusted in each case according to the type of monomer used so as to obtain an almost complete conversion within a reasonable time. Temperatures of 40 to 120 ° C and times of 4 to 48 hours are well suited, and preferably 70 to 100 ° C and 12 to 36 hours.
- the third step in the production of the organophosphonic polymers according to the invention consists in subjecting the polymer obtained to acid or alkaline hydrolysis of the ester functions. In order to achieve a high conversion rate, it is necessary to achieve drastic conditions during hydrolysis. In general, this is done using concentrated aqueous solutions of inorganic acid or inorganic base.
- the hydrolysis step is preferably carried out under an atmosphere of an inert gas such as nitrogen and at temperatures included between 40 and 100 ° C. When the temperature is between 60 and 90 ° C, the reaction times are generally between 4 and 12 hours.
- the invention also relates to aqueous solutions of hydrogen peroxide stabilized by means of said organophosphonic polymers against decomposition in oxygen and in water.
- Aqueous solution of hydrogen peroxide is meant any aqueous solu'.ion of hydrogen peroxide whose weight concentration is between 0.1 and 99 g H 2 O 2/100 g of solution and preferably, between 0.5 and 95 X.
- this solution may be a solution commer ⁇ cial weight concentration of hydrogen peroxide of between 25 and 70 g H 0 2/100 g solution.
- Y represents the methyl group or a hydrogen atom and that Z represents an alkali metal atom.
- organophosphonic polymer which has given particularly advantageous results as stabilizer in aqueous solutions of hydrogen peroxide is the poly- ⁇ - (hydroxyvinylphosphonate) of Na.
- the optimal content of organophosphonic polymer in aqueous solutions of hydrogen peroxide depends on various parameters, in particular on the concentration of the solution in hydrogen peroxide, on its pH as well as on the organophosphonic polymer selected.
- the aqueous hydrogen peroxide solution contain at least 0.5 mg of organophosphonic polymer per kg of solution, and preferably not more than 2500 mg.
- the preferred contents are between 1 and 300 mg per kg of solution.
- the invention applies equally to solutions of hydrogen peroxide which are acidic, neutral or basic. It finds in particular an advantageous application for acid solutions whose pH is between 2 and 5.
- H 2 0 2 solutions for cleaning glasses optics in particular contact lenses
- H 2 0 2 solutions for hydrometallurgy in particular in metal extraction by leaching of ores
- H 2 0 2 solutions for etching pickling and metal polishing (for example, baths for the chemical polishing of copper, such as those described in patent application FR-A-87.13407 (SOLVAY & Cie)
- H 2 0 2 solutions used for protection of the environment such as those used to detoxify liquid or gaseous effluents and those used for water purification
- H 2 0 2 solutions used in the food industry and, in particular, those used for the disinfection of packaging and containers.
- the aqueous solution of hydrogen peroxide may be an aqueous bleaching bath containing hydrogen peroxide in the concen ⁇ tration of between 0.5 and 50 g H 2 0 2/100 g of solution.
- bleaching baths are washing liquors or hydrogen peroxide bleaching of textile materials and hydrogen peroxide bleaching liquors of paper pulps.
- the invention also relates to the use of said organophosphonic polymers for stabilizing aqueous solutions of hydrogen peroxide.
- the invention has the advantage of providing aqueous solutions of hydrogen peroxide, the long-term stability of which is improved with respect to the decomposition induced by the heavy metal and transition cations compared with known organic polymer stabilizers. . Examples not The following limits are given for the purpose of illustrating the invention.
- Example i synthesis of poiy- - (hydroxyvinylphosphonate) step: preparation of diethyl-1-acetoxyvinylphosphonate 110 ml of dry toluene were introduced into a 250 ml glass flask in which 110.4 g (0.8 mole) of diethylphosphite and 0.8 ml of boron trifluoride etherate. The ketene gas prepared from acetone was then bubbled through the solution through a sintered glass orifice. The temperature of the solution was allowed to rise to 55 ° C and then kept at about 50 ° C using an external cooler.
- the ketene which escaped from the flask was returned to the reaction medium by means of a distillation device operating with dry ice. After 2 hours of reaction, 76.7 g of ketene were condensed in the reaction medium. 2 g of anhydrous Na 2 CO 3 were then added to the solution, which was distilled under vacuum through a 15 cm long Vigreux column.
- a 1.85 M polymer solution from the second step was also treated with 12 N NaOH for 6 hours at 90 ° C under a nitrogen atmosphere.
- the mixture was then neutralized using 4N HCl until the pH dropped to 4.2 and diluted with distilled water to a hydrolysed polymer content of 2.28 g / 21, 5 g of solution.
- Examples 2R to 7 • Passivation of the apparatus:
- the apparatus used in all of the following examples has undergone a passivation treatment beforehand in order to eliminate the disturbing effect of the impurities adsorbed on the surface in contact with the stabilized hydrogen peroxide solutions used.
- the pH of each solution was adjusted using HNO3 or NaOH to a value of 3.0 for the 35% H2O2 solution and 1.3 for the 70% solution.
- the solutions were stored at room temperature and their H 2 O 2 titer was determined periodically during the time by conventional iodometric analysis.
- a known hydroxylated organic polymer namely poly- ⁇ - (hydroxymethyl acrylate) and two grades of Na poly- ⁇ - (hydroxyvinylphosphonate) Na according to the invention, one being obtained by means of acid hydrolysis in the third manufacturing step (product PHVP (a) of Example 1) and the other by means of alkaline hydrolysis (product PHVP ( b)).
- COD chemical oxygen demand
- BOD5 biological oxygen demand
- Example 8R was carried out, for comparison, with the known hydroxylated organic polymer, namely poly- ⁇ (hydroxyacrylate) of Na (PHAS) and two grades of poly- ⁇ (hydroxyvinylphosphonate) of Na according to the invention, one being obtained by means of acid hydrolysis in the third manufacturing step (PHVP sample (a) of Example 1) and the other by means of alkaline hydrolysis (PHVP sample ( b)).
- the known hydroxylated organic polymer namely poly- ⁇ (hydroxyacrylate) of Na (PHAS) and two grades of poly- ⁇ (hydroxyvinylphosphonate) of Na according to the invention, one being obtained by means of acid hydrolysis in the third manufacturing step (PHVP sample (a) of Example 1) and the other by means of alkaline hydrolysis (PHVP sample ( b)).
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polymerisation Methods In General (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/030,461 US5447979A (en) | 1990-10-02 | 1991-09-09 | Organophosphonic polymers and their use as stabilisers for aqueous hydrogen peroxide solutions |
BR919107101A BR9107101A (pt) | 1990-10-02 | 1991-09-24 | Polimeros organofosfonicos,processo de fabricacao dos mesmos,solucao aquosa de peroxido de hidrogenio e utilizacao de um polimero organofosfonico |
DE69105745T DE69105745T2 (de) | 1990-10-02 | 1991-09-24 | Organophosphonpolymere und verwendung davon zur stabilisierung von wässrigen lösungen aus wasserstoffperoxid. |
AU86216/91A AU657495B2 (en) | 1990-10-02 | 1991-09-24 | Organophosphonic polymers and their use as stabilizers for aqueous solutions of hydrogen peroxyde |
EP91916926A EP0551317B1 (fr) | 1990-10-02 | 1991-09-24 | Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene |
NO931263A NO931263D0 (no) | 1990-10-02 | 1993-04-01 | Organofosfinsyrepolymerer og anvendelse av disse som stabilisatorer for hydrogenperoksyd |
FI931479A FI931479A (fi) | 1990-10-02 | 1993-04-01 | Organofosfonsyrapolymerer och dess anvaendning som stabilisatorer i vattenloesningar av vaeteperoxid |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9000935A BE1003944A3 (fr) | 1990-10-02 | 1990-10-02 | Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene. |
BE9000935 | 1990-10-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992006122A1 true WO1992006122A1 (fr) | 1992-04-16 |
Family
ID=3884951
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/001846 WO1992006122A1 (fr) | 1990-10-02 | 1991-09-24 | Polymeres organophosphoniques et leur utilisation comme stabilisants de solutions aqueuses de peroxyde d'hydrogene |
Country Status (14)
Country | Link |
---|---|
US (1) | US5447979A (fr) |
EP (1) | EP0551317B1 (fr) |
AT (1) | ATE115152T1 (fr) |
AU (1) | AU657495B2 (fr) |
BE (1) | BE1003944A3 (fr) |
BR (1) | BR9107101A (fr) |
CA (1) | CA2092991A1 (fr) |
DE (1) | DE69105745T2 (fr) |
ES (1) | ES2065704T3 (fr) |
FI (1) | FI931479A (fr) |
NZ (1) | NZ240045A (fr) |
PT (1) | PT99129B (fr) |
WO (1) | WO1992006122A1 (fr) |
ZA (1) | ZA917854B (fr) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB933107A (en) * | 1959-11-11 | 1963-08-08 | Hoechst Ag | Vinylphosphonic acid polymers and process for making them |
US3943074A (en) * | 1973-06-08 | 1976-03-09 | S.A. Texaco Belgium N.V. | Vinyl phosphonic acid-divinyl sulfone copolymer ion exchange resin |
GB2090265A (en) * | 1980-12-31 | 1982-07-07 | Colgate Palmolive Co | Antigingivitis activity |
EP0309031A1 (fr) * | 1987-09-25 | 1989-03-29 | Solvay | Bains et procédé pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre |
US4822861A (en) * | 1988-03-15 | 1989-04-18 | Polychrome Corporation | Method for the preparation of polyvinyl phosphonic acid |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB853008A (en) * | 1958-06-20 | 1960-11-02 | Ici Ltd | Polymers containing phosphorus |
US3227696A (en) * | 1960-02-26 | 1966-01-04 | Shell Oil Co | Phosphorous and chlorine-containing copolymers as lubricant additives |
NL129043C (fr) * | 1964-08-14 | |||
US3920570A (en) * | 1970-12-17 | 1975-11-18 | Solvay | Sequestration of metal ions by the use of poly-alpha-hydroxyacrylates |
LU62270A1 (fr) * | 1970-12-17 | 1972-08-23 | ||
DE3245541A1 (de) * | 1982-12-09 | 1984-06-14 | Cassella Ag, 6000 Frankfurt | Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung |
DE3248031A1 (de) * | 1982-12-24 | 1984-06-28 | Cassella Ag, 6000 Frankfurt | Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung |
DE3248019A1 (de) * | 1982-12-24 | 1984-06-28 | Cassella Ag, 6000 Frankfurt | Wasserloesliche copolymerisate, ihre herstellung und ihre verwendung |
CA2005640A1 (fr) * | 1988-12-29 | 1990-06-29 | Theodore A. Del Donno | Compositions polymeriques phosphorees renfermant des composes metalliques polyvalents hydrosolubles |
FR2650594B1 (fr) * | 1989-08-04 | 1992-04-03 | Coatex Sa | Application aux suspensions aqueuses pigmentaires de carbonate de calcium d'un agent polycarboxylique a fonction phosphatee ou phosphonee inhibant l'effet de choc provoque par l'introduction d'un electrolyte sous forme concentree |
US5109033A (en) * | 1991-05-16 | 1992-04-28 | Arco Chemical Technology, L.P. | Vinyl aromatic monomer/vinyl phosphonate copolymer compositions and foamed articles derived therefrom |
DE4142731A1 (de) * | 1991-12-21 | 1993-06-24 | Hoechst Ag | Biozide polymerisate und polymerisatdispersionen, verfahren zu ihrer herstellung und ihre verwendung |
-
1990
- 1990-10-02 BE BE9000935A patent/BE1003944A3/fr not_active IP Right Cessation
-
1991
- 1991-09-09 US US08/030,461 patent/US5447979A/en not_active Expired - Fee Related
- 1991-09-24 AT AT91916926T patent/ATE115152T1/de not_active IP Right Cessation
- 1991-09-24 WO PCT/EP1991/001846 patent/WO1992006122A1/fr active IP Right Grant
- 1991-09-24 BR BR919107101A patent/BR9107101A/pt not_active Application Discontinuation
- 1991-09-24 EP EP91916926A patent/EP0551317B1/fr not_active Expired - Lifetime
- 1991-09-24 AU AU86216/91A patent/AU657495B2/en not_active Ceased
- 1991-09-24 ES ES91916926T patent/ES2065704T3/es not_active Expired - Fee Related
- 1991-09-24 CA CA002092991A patent/CA2092991A1/fr not_active Abandoned
- 1991-09-24 DE DE69105745T patent/DE69105745T2/de not_active Expired - Fee Related
- 1991-10-01 NZ NZ240045A patent/NZ240045A/en unknown
- 1991-10-01 ZA ZA917854A patent/ZA917854B/xx unknown
- 1991-10-01 PT PT99129A patent/PT99129B/pt not_active IP Right Cessation
-
1993
- 1993-04-01 FI FI931479A patent/FI931479A/fi not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB933107A (en) * | 1959-11-11 | 1963-08-08 | Hoechst Ag | Vinylphosphonic acid polymers and process for making them |
US3943074A (en) * | 1973-06-08 | 1976-03-09 | S.A. Texaco Belgium N.V. | Vinyl phosphonic acid-divinyl sulfone copolymer ion exchange resin |
GB2090265A (en) * | 1980-12-31 | 1982-07-07 | Colgate Palmolive Co | Antigingivitis activity |
EP0309031A1 (fr) * | 1987-09-25 | 1989-03-29 | Solvay | Bains et procédé pour le polissage chimique de surfaces en cuivre ou en alliage de cuivre |
US4822861A (en) * | 1988-03-15 | 1989-04-18 | Polychrome Corporation | Method for the preparation of polyvinyl phosphonic acid |
Also Published As
Publication number | Publication date |
---|---|
EP0551317B1 (fr) | 1994-12-07 |
ES2065704T3 (es) | 1995-02-16 |
CA2092991A1 (fr) | 1992-04-03 |
PT99129A (pt) | 1992-08-31 |
US5447979A (en) | 1995-09-05 |
BR9107101A (pt) | 1994-03-08 |
ATE115152T1 (de) | 1994-12-15 |
ZA917854B (en) | 1992-07-29 |
DE69105745D1 (de) | 1995-01-19 |
FI931479A0 (fi) | 1993-04-01 |
AU657495B2 (en) | 1995-03-16 |
AU8621691A (en) | 1992-04-28 |
BE1003944A3 (fr) | 1992-07-22 |
NZ240045A (en) | 1992-07-28 |
PT99129B (pt) | 1999-03-31 |
FI931479A (fi) | 1993-04-01 |
DE69105745T2 (de) | 1995-04-27 |
EP0551317A1 (fr) | 1993-07-21 |
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