EP1276744A1 - Acides n-alpha ,n-omega -dialkyle aminomethylenephosphoniques et leur utilisation - Google Patents

Acides n-alpha ,n-omega -dialkyle aminomethylenephosphoniques et leur utilisation

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Publication number
EP1276744A1
EP1276744A1 EP01930576A EP01930576A EP1276744A1 EP 1276744 A1 EP1276744 A1 EP 1276744A1 EP 01930576 A EP01930576 A EP 01930576A EP 01930576 A EP01930576 A EP 01930576A EP 1276744 A1 EP1276744 A1 EP 1276744A1
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EP
European Patent Office
Prior art keywords
carbon atoms
independently
group
formula
dialkyl
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.)
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Application number
EP01930576A
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German (de)
English (en)
Inventor
Druce K. Crump
David A. Wilson
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication date
Application filed by Dow Global Technologies LLC filed Critical Dow Global Technologies LLC
Publication of EP1276744A1 publication Critical patent/EP1276744A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds
    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • 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
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen

Definitions

  • Polyaminophosphonic acid compounds are known to have utility in a wide range of applications such as scale deposition prevention agents, detergent formulations, stabilizing agents in peroxygen bleaching of cellulosic materials such as textiles and wood pulp, and as metal ion control agents in a variety of other applications.
  • U.S. Patent 3,639,645 discloses scale inhibiting compositions for use in water treatment that include amino-methylenephosphonic acids and hydroxycarboxylic acids . While the generic structure of the aminomethylenephosphonic acids disclosed by Miller et al encompasses a great number of both non-N-alkylated and N-alkylated aminomethylenephosphonic acids, only experimental data for a single non-N-alkylated amino- methylenephosphonic acid, EDTMP (ethylenediamine tetramethylenephosphonic acid has been provided by Miller et al . No N-alkylated compounds were prepared or tested.
  • U.S. Patent 4,652,403 (May et al) describes detergent compositions that contain a water-insoluble aluminosilicate and an aminopoly (methylenephosphonate) component which is a mixture of ethylenediamine or diethylenetriamine phosphonic acid derivatives .
  • an aminopoly (methylenephosphonate) component which is a mixture of ethylenediamine or diethylenetriamine phosphonic acid derivatives .
  • small quantities of N-methyl structures of ethylenediamine or diethylenetriamine phosphonic acid derivatives may form during standard industrial synthesis, these N-methyl compounds are generally regarded as undesirable impurities.
  • no example or experimental data for such N-alkylated phosphonic acid derivatives is given by May et al .
  • partially phosphonomethylated amines are regarded as less effective than their fully phosphonomethylated counterparts in applications such as water treatment, corrosion and scale inhibition, scale removal and peroxide stabilization in pulp and paper.
  • diethylenetriamine penta methylenephosphonic acid
  • diethylenetriamine tri methylenephosphonic acid
  • the partially phosphonomethylated derivative of diethylenetriamine is less effective on an equal weight basis.
  • the present invention concerns a peroxide bleaching composition
  • a peroxide bleaching composition comprising at least one N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acid having the following formula I
  • R is an alkylene group having from 2 to 6, preferably 2 to 4, carbon atoms
  • Ri and R 2 are each independently an alkyl group having from 1 to 6, preferably 1 to 4, carbon atoms, a hydroxyalkyl group having alkyl of from 1 to 6, preferably 1 to 4, carbon atoms, or carboxyalkyl group having alkyl of from 1 to 6, preferably from 1 to 4, carbon atoms
  • M is, independently in each occurrence, selected from the group consisting of H, NH 4 , amine, alkali metal, alkaline earth metal, or a linear or branched alkyl group having from 1 to 4 carbon atoms
  • n is an integer from 1 to 6.
  • the present invention concerns a detergent composition
  • a detergent composition comprising at least one N ,N ⁇ -dialkyl aminomethylenephosphonic acid having the formula I hereinbefore, or N-oxide thereof having the formula II or formula III hereinbefore, wherein R, Ri, R 2 , M and n are as defined hereinbefore.
  • the present invention concerns a metal ion chelating composition
  • a metal ion chelating composition comprising at least one N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acid having the formula I hereinbefore, or N-oxide thereof having the formula II or formula III hereinbefore, wherein R, Ri, R 2 , M and n are as defined hereinbefore.
  • the present invention concerns an improved process for bleaching a cellulosic material which process comprises contacting the cellulosic material with a peroxide bleaching composition, the improvement comprising the use in the peroxide bleaching composition of at least one N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acid having the formula I hereinbefore, or N-oxide thereof having the formula II or formula III hereinbefore, wherein R, Ri, R 2 , M and n are as defined hereinbefore, in an amount effective to stabilize a peroxide in said bleaching composition.
  • the present invention concerns an improved process for the inhibition of corrosion and scale deposits or for the removal of scale deposits in water treatment and oil field applications such as crude oil and natural gas recovery operations, the improvement comprising contacting corrosion and scale forming species or scale deposits with a composition comprising at least one N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acid having the formula I hereinbefore, or N-oxide thereof having the formula II or formula III hereinbefore, wherein R, Ri, R 2 , M and n are as defined hereinbefore, in an amount effective to inhibit corrosion and scale deposition or remove scale deposits.
  • the alkylene group having from 2 to 6 carbon atoms contemplated by R in formulas I, II and III can be a straight or branched chain alkyl group.
  • Non-limiting examples of such alkylene groups are ethylene, n- propylene, isopropylene, n-butylene, sec-butylene, n- pentylene, and n-hexylene.
  • the alkylene group is ethylene, n-propylene, isopropylene, n-butylene, and sec-butylene.
  • the alkylene group is such that the distance between the nitrogens is two carbons, such as ethylene, isopropylene, or the like.
  • the alkyl group having from 1 to 4 carbon atoms contemplated by M in formulas I, II and III can be a straight or branched chain alkyl group.
  • Non-limiting examples of such alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, and sec-butyl.
  • the alkali metal contemplated by M in formulas I, II and III is preferably sodium, potassium or lithium.
  • M is preferably H, NH 4 , sodium, potassium or calcium, more preferably H, NH 4 , and sodium.
  • N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore are conveniently prepared by methods known in the art.
  • a suitable alkylating agent such as alkyl iodide
  • the alkylated product obtained is subsequently hydrolyzed to remove the tosyl groups in accordance with the procedure described in Inorg. Chem . , Vol. 34, page 1409.
  • N ⁇ ,N ⁇ -dialkyl diethylenetriamine thus obtained is then phosphonomethylated by reacting it with phosphorous acid and formaldehyde using conditions known in the art to produce N ,N ⁇ -dialkyl aminomethylenephosphonic acids of formula I .
  • Th N-oxides of N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acids of formulas II and III hereinabove are conveniently prepared according to known procedures for oxidizing amines.
  • amine oxides are prepared by oxidizing an amine with a suitable oxidizing agent such as hydrogen peroxide. The oxidation can be carried out in aqueous solutions. See, for example, U.S. Patent No. 3,470,243.
  • the bleaching compositions of the present invention may be used in variuos bleaching applications such as, for example, bleaching of textiles, brightening or delignification of wood pulp, stain removal, and photographic processing.
  • the bleach bath may be comprised of components including water, hydrogen peroxide, sodium persulfate, sodium hydroxide, wetting agent (nonionic, cationic, anionic, or zwitterionic surfactant), and bleach stabilizer ingredients.
  • Other ingredients that may also be used include optical brighteners, magnesium salts, chelants such as aminocarboxylic acid and/or hydroxycarboxylic acid, silicates, thickening agents, viscosity controlling agents, and dispersants.
  • the bleach bath may be combined as a wash stage, and the treatment may be performed on dyed or non-dyed fabrics.
  • hydrogen peroxide When hydrogen peroxide is employed, its composition may range from about 0.5 to 5 percent by weight in the bleach bath; sodium hydroxide may be present in a range from about 0.5 to about 10 percent by weight; wetting agent may be present from about 0.1 to about 5 percent by weight; stabilizer adjuncts such as hydroxycarboxylic acids may be present from about 0.01 to about 0.5 percent by weight; other ingredients such as brighteners, silicates, and dispersants each may typically compose less than about 5 percent by weight of the bleach bath. Water is present in the greatest amount, at up to about 95 percent by weight of the bleach bath composition.
  • Peroxide agents are also widely employed in the bleaching of wood pulp.
  • Hydrogen peroxide is the most widely used peroxide agent used for brightening of wood pulp.
  • a typical peroxide bleaching stage of wood pulp may be performed under a pressure of about 5 atmospheres using ambient air or oxygen gas, as well as at ambient atmospheric pressures.
  • Hydrogen peroxide may be used at a dose rate on Oven Dried pulp (O.D. pulp) of from about 0.1% to 10% in the peroxide bleaching stage.
  • the wood pulp may be derived from a chemical pulp process, mechanical or groundwood pulp process, chemi- thermomechanical pulp process, or other process variation familiar to those in the art.
  • the N ⁇ ,N ⁇ -dialkyl aminomethylene-phosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore are used at from about 0.05 percent to about 0.5 percent on O.D. pulp.
  • the N ⁇ ,N ⁇ -dialkyl aminomethylene-phosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore are used from about 0.005 percent to about 0.2 percent on O.D. pulp.
  • the advantage of the compounds of the invention is that significantly less is needed than conventional phosphonic acid products, thus offering a cost advantage and reducing nitrogen and phosphorus in bleach plant effuents.
  • a pulp bleaching process may include several stages. Some of the pulp bleaching stages that may be encountered in chemical pulp processes include oxygen, chlorine dioxide, ozone, hydrogen peroxide, pressurized hydrogen peroxide, peroxymonosulfate, peracetic acid, and others.
  • the N ⁇ ,N ⁇ -dialkyl aminomethylene-phosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore may be employed within or prior to any of these stages, while the stages that would benefit most from their use are those stages that employ hydrogen peroxide.
  • Some of the bleaching stages that may be encountered in mechanical pulping and deinking processes include hydrosulfite, formamidinesulfinic acid, and hydrogen peroxide.
  • Bleaching agents may be added in a bleaching tower, as a part of the refining process, or in a repulper.
  • the use of N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N- oxides represented by formulas II and III hereinbefore results in an improvement in all mechanical pulp and deinking pulp bleaching stages.
  • peroxide bleaching of pulp there may be other components present in addition to water, pulp, hydrogen peroxide, and stabilizer. These components may include chemicals that were added to the pulp in previous stages or those that are added with the bleach liquor. Such substances that may be added with the bleach liquor include magnesium salts, silicates, other complexing agents such as aminocarboxylic acids, hydroxycarboxylic acids, water-soluble polymers, zeolites, carbonate salts, or bleaching catalysts . Examples of some bleaching catalysts are descrbed in U.S. Pat. 6,136,223.
  • N ⁇ ,N ⁇ -dialkyl aminomethylene-phosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore in detergent compositions enhances of peroxide bleaching components and facilitate the removal of various food stains from fabrics during laundering operations .
  • the detergent compositions of the present invention comprise from about 0.01 to about 15, preferably from about 0.05 to about 5 percent by weight of at least one N ⁇ ,N ⁇ -dialkyl aminomethylene-phosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore; from about 1 to about 80, preferably from about 10 to about 50, percent by weight of a detergent surfactant selected from nonionic, anionic, cationic, zwitterionic, and ampholytic surfactants and mixturtes thereof; and from about 5 to about 80, preferably from about 10 to about 50 percent by weight of a detergent builder.
  • Nonionic surfactants that are suitable for use in the present invention include those that are disclosed in U.S. Patent No. 3,929,678. Included, without limitation, are the condensation products of ethylene oxide with aliphatic alcohols, the condensation of ethylene oxide with the base formed by the condensation of propylene oxide and propylene glycol or the product formed by the condensation of propylene oxide and ethylendiamine . Also included are the various polyethylene oxide condensates of alkyl phenols and various amine oxide surfactants . Anionic surfactants that are suitable for use in the present invention are described in U.S. Patent No. 3,929,678. These include, without limitation, sodium and potassium alkyl sulfates; various salts of higher fatty acids, and alkyl polyethoxylate sulfates.
  • Cationic surfactants that may be used are described in U.S. Patent No. 4,228,044.
  • Preferred cationic surfactants are the quaternary ammonium surfactants .
  • ampholytic and zwitterionic surfactants such as those taught in U.S. Patent No. 3,929,678 can be used in the present invention.
  • Suitable builder substances are for example: wash alkalis, such as sodium carbonate and sodium silicate, or complexing agents, such as phosphates, or ion exchangers, such as zeolites, and mixtures thereof.
  • the builder component may further contain cobuilders .
  • cobuilders In modern detergents, it is the function of cobuilders to undertake some of the functions of phosphates, for example sequestration, soil antiredeposition and primary and secondary washing action.
  • the builder components may contain, for example water- insoluble silicates, as described for example in German Laid-Open Application DE-OS No. 2.412.837, and/or phosphates.
  • other phosphorus-containing organic completing agents are suitable for use as further detergent ingredients .
  • detergent additives include aminotrismethylenetriphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, 1- hydroxyethanc-1, 1-diphosphonic acid, phosphonoacetic and phosphonopropionic acid, copolymers of vinylphosphonic acid and acrylic and/or maleic acid and also partially or completely neutralized salts thereof.
  • organic compounds which act as builders that may be present in detergent formulations are polycarboxylic acids, hydroxycarboxylic adds and aminoocarboxylic acids which are usually used in the form of their water-soluble salts .
  • Preferred cobuilder substances arc polymeric carboxylates .
  • These polymeric carboxylic acids include the carboxymethyl ethers of sugars, of starch and of cellulose. Zeolites and phosphates are also useful.
  • Particularly important polymeric carboxylic acids are for example, the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid, citraconic acid and, the copolymers between the aforementioned carboxylic acids.
  • Bleaching agents that can be used are in particular hydrogen peroxide and derivatives thereof or available chlorine compounds .
  • bleaching agent compounds which provide H 2 0 2 in water, sodium perborate hydrates, such as NaB0 2 • H 2 0 2 • 3H 2 0 and NaB0 2 -H 2 0 2 and percarbonates such as 2Na 2 C0 3 - 3H 2 0 2 are of particular importance.
  • These compounds can be replaced in part or in full by other sources of active oxygen, in particular by peroxyhydrates, such as peroxyphosphonates, citrate perhydrates, urea, H 2 0 2 - providing peracid salts, for example, caroates, perbenzoates or peroxyphthalates or other peroxy compounds .
  • customary water-soluble and/or water-insoluble stabilizers for peroxy compounds can be incorporated together with the former in amounts from 0.25 to 10 percent by weight, based on the peroxy compound.
  • Suitable water-insoluble stabilizers are magnesium silicates with MgO:Si0 2 in a* ratio of from 4:1 to 1:4, preferably from 2:1 to 1:2, in particular 1:1 in composition, usually obtained by precipitation from aqueous solutions.
  • Other alkaline earth metals of corresponding composition can also be suitably used.
  • bleach activators in the detergent, advantageously in an amount from 5 to 30 percent by weight, based on the H 2 0 2 -providing compound.
  • the bleaching agents used can also be active chlorine compounds of the inorganic or organic type.
  • suitable foam regulants such as soaps
  • nonsurfactant-like foam inhibitors such as propoxylated and/or butoxylated aminotriazines
  • suitable nonsurfactant-like foam inhibitors are organic compounds, such as paraffins, aliphatic carboxylic esters; they can be used in particular in combinations of surfactants of the sulfate and/or sulfonate type with soaps for foam inhibition.
  • the detergents may contain optical brighteners such as derivatives of diaminostilbenedisulfonic acid, 1,3- diarylpyrazolines, or products of the class of the substituted styryls, ethylenes, thiophenes, naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins and naphthalimides .
  • optical brighteners such as derivatives of diaminostilbenedisulfonic acid, 1,3- diarylpyrazolines, or products of the class of the substituted styryls, ethylenes, thiophenes, naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins and naphthalimides .
  • laundry detergent compositions of the present invention also contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
  • Amylase and protease enzymes suitable for use in detergents are well known in the art and in commercially available liquid and granular detergents .
  • Commercial detersive enzymes preferably a mixture of amylase and protease are typically used at levels of from about 0.001 to about 2 weight percent, and higher, in the present detergent compositions.
  • N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore are effective for corrosion and scale control in aqueous systems at application rates of from as low as sub-part per million levels and up to about 2 percent.
  • the effectiveness at extremely low levels for scale deposit prevention is due to their "threshold effect" at substoichiometric concentrations, that is, they are capable of keeping insoluble salts kinetically inhibited from precipitation, or on the "threshold” of precipitation.
  • somewhat greater dose levels of N ⁇ ,N m -dialkyl aminomethylenephosphonic acids are required for corrosion protection in order to achieve a passive film on the metal surface. Once the passivation of the metal surface has been achieved, the dose rate -can be lowered to the low ppm range in the aqueous system.
  • the corrosion and scale inhibiting compositions of the present invention may also contain other compounds.
  • the other components present may include other corrosion protection agents such as molybdates, chromates, zinc, tolytriazole, or benzotriazole, to name a few.
  • Other scale and deposit prevention additives may include terpolymers, copolymers, and homopolymers of acrylic acid, maleic acid, succinic acid, epoxysuccinic acid, aspartic acid, and other suitable monomers well known to those skilled in the art.
  • phosphonic acid compounds such as aminotrismethylenephosphonic acid, ethylenediaminetetra-methylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, phosphonobutanetricarboxylic acid, phsophonosuccinic acid, hydroxyphosphonoacetic acid, or others.
  • Conventional complexing agents and their water soluble salts may also be added, such as the aminocarboxylic acids, hydroxycarboxylic acids, phosphoric acid, silicic acid, and others.
  • Biocides are also often employed in corrosion and scale treatment programs. The level of additives for corrosion and scale prevention is typically kept as low a possible to minimize cost. Thus, dose rates of the various ingredients used for corrosion and scale control are applied at rates of less than about 1000 ppm, typically at dose rates of 100 ppm or less.
  • the corrosion and scale inhibition compounds may be added on a continuous or interval basis.
  • Scale and corrosion prevention agents in the oilfield may be applied as concentrated solutions as an interval treatment' or applied continuously at dose rates of up to about 1000 ppm in the aqueous stream.
  • One type of interval treatment for scale prevention or scale removal in the oilfield is a squeeze treatment.
  • a squeeze treatment a solution of a scale prevention composition comprising at least one N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore is pumped down hole and "squeezed" into the pores of the formation around the well bore.
  • An ingredient designed to favorably deposit the scale prevention agent to the formation surfaces may be added as a part of the inhibitor squeeze treatment or as a separate squeeze treatment.
  • Agents that may be used with the N ,N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore to achieve the desired characteristics of a squeeze treatment may include salts of aluminum, iron, magnesium, copper, or others; gycol ethers, various polymers, and salts of conventional chelating agents such as aminophosphonic acids, hydroxycarboxylic acids, or aminocarboxylic acids.
  • the N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore prevent water-formed scale deposits such as calcium carbonate, calcium sulfate, calcium oxalate, and barium sulfate.
  • the effective dose for scale prevention may be affected by the level and nature of cations and anions present in the water system, as well as the pH and the temperature.
  • the N ⁇ , N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore are effective at temperatures up to about 300 °C, and pH range from about 3 to 14.
  • N ⁇ ,N ⁇ - dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore have the ability to control metal ions very effectively at elevated pH, where standard aminocarboxylic acids may fail to function effectively.
  • N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acids of formula I hereinbefore and their N-oxides represented by formulas II and III hereinbefore are effective as chelants for metal ions.
  • effectiveness as a chelant is conveniently measured by complexing the chelant with a metal ion such as by mixing an aqueous solution of known concentration of the chelant with an aqueous solution containing metal ions of known concentration and measuring chelation capacity by titrating the chelant with a metal ion in the presence of an indicator dye, using as an endpoint detector a photosensitive electrode.
  • N,N' ' -dimethyl diethylenetriamine N,N',N'- tri (methylenephosphonic acid) was prepared by first preparing the tri-tosyl derivative of diethylenetriamine (Ts 3 dien) . The Ts 3 dien was then alkylated on the terminal nitrogen atoms using methyl iodide to prepare N,N''- dimethyl diethylenetriamine Me 2 Ts 3 dien. Me 2 Ts 3 dien) was then hydrolyzed via HBr-HOAc to remove the tosyl groups and yield N,N' ' -dimethyldiethylenetriamine (Me 2 dien) . The synthesis technique used as a guide is described in Inorg. Chem . , Vol. 34, page 1409.
  • the N,N' ' -dimethyldiethylenetriamine was then phosphonomethylated by reacting it with phosphorous acid and formaldehyde using conditions known in the art .
  • the aqueous product solution produced in this manner had an organic purity of greater than 95 percent N, ' ' -dimethyl diethylenetriamine N,N' ,N' ' -tri (methylenephosphonic acid) (s-Me 2 DTTP) .
  • the s-Me 2 DTTP in acidic D 2 0 solution showed singlet peaks in the 31 P NMR spectrum at 8.39 ppm and 11.72 ppm, representing the P atom of the two terminal N phosphonic acid groups and P atom on the center N phosphonic acid group respectively. The peaks integrated in a 2:1 ratio, in agreement with the theoretical structure.
  • the 31P spectrum of the product solution also showed a small peak at 4.97 ppm representing a small amount of residual H 3 P0 3 starting material and a very small peak at 22.34 ppm representing a trace amount of hydroxymethylenephosphonic acid (reaction product of formaldehyde and H 3 P0 3 ) .
  • Organic purity of the product from the phosphorous NMR is greater than 95 percent as s-Me 2 DTTP.
  • the 1H NMR spectrum in acidic D 2 0 showed a group of peaks representing the protons of the amine backbone and the phosphonomethyl methylenes from about 2.8 ppm to 3.3 ppm. A sharp singlet at 2.55 ppm represents the terminal N-methyl protons . Integration of the backbone and phosphonomethyl methylene protons and the N-methyl protons showed the predicted ratio of 14 to 6. There were very small peaks at 4.25 and 7.73 ppm representing the split signal from the residual H P0 3 raw material P-bonded proton. Purity based on the proton NMR is greater than 95 percent as s-Me 2 DTTP.
  • the 13 C NMR also supports the preparation of an essentially pure N, N' ' -dimethyldiethylenetriamine- N,N' , N' ' -tri (methylenephosphonic acid) .
  • the activity of the aqueous product solution was verified by titration, nitrogen analysis, and NMR techniques to be 34.4 percent active as essentially pure N, N' ' -dimethyldiethylene- triamine-N,N /' N' ' -tri (methylenephosphonic acid) .
  • the s- Me 2 DTTP thus produced was used in the subsequent examples of the invention.
  • N,N' ' -diethyldiethylenetriamine-N,N' ,N' ' - tri (methylenephosphonic acid) was prepared using the above procedure, except that ethyl iodide was used as the N- alkylating agent instead of methyl iodide.
  • the desired phosphonic acid structure was verified by 31P NMR, 1H NMR, and 13CNMR spectra.
  • N,N' ' ' -dimethyl-triethylenetetra-amine-N,N' , N' ' ,N' ' ' - tetra (methylene-phosphonic acid) was prepared using the procedure outlined for synthesis of Compound 1 except that the tetra-tosyl derivative of linear triethylenetetraamine was prepared as the initial synthetic step.
  • the desired phosphonic acid structure was verified by 31P NMR, 1H NMR, and 13CNMR spectra.
  • N,N' ' -dimethyldiethylenetriamine N,N' , N' ' - tri (methylenephosphonic acid) tris was prepared by taking the a portion of the 34.4 percent active solution of s-Me 2 DTTP (preparation described above) and removing the bulk of the water and free acid by rotary evaporation. After the first evaporation, the glassy solid was re-dissolved in water and the water evaporated once again. The resulting light yellow glassy solid was dissolved using water and NaOH to provide a solution with a pH of about 10 and a solids content of about 40 percent.
  • Comparative compounds DTPMP, EDTMP, HMDTMP, AMP, Dequest 2086, MEA-phos, Bricorr 288, HEDP, and PBTCA were obtained from their respective commercial sources and were used according to the manufacturer's claimed percent actives content .
  • DTPMP is generally regarded as one of the most effective peroxide stabilizing additives known.
  • DTPMP is particularly effective alone or in combination with other components in peroxide use in textile, detergent, and pulp bleaching.
  • Comparative compounds TTHMPA, DPTPMP, MMA-phos, EDA- BP-phos, u-Me 2 EDDP, u-Me 2 DTTP, and s-Me 2 EDDP were synthesized from commercially obtained amines (Aldrich Chemical Co.) and their respective phosphonic acid derivatives were prepared by reacting the amine with phosphorous acid and formaldehyde using conditions known in the art. Each was fully phosphonomethylated based on the available amino hydrogens of the amine molecule .
  • Comparative compound Silicate is commercially available PQ-N silicate solution. Silicate is often used as a peroxide stabilizer in various applications such as peroxide use in textile, detergents, and pulp and paper operations .
  • the pulp slurry was then treated with a 39 percent active Na 4 EDTA aqueous solution (sold by The Dow Chemical Company under the trademark VERSENE 100 chelating agent) at a dosage of 0.5 percent based on the O.D. weight of pulp at 65 °C for one hour.
  • VERSENE 100 chelating agent 39 percent active Na 4 EDTA aqueous solution
  • bleach liquor was prepared in a separate bottle.
  • a 28 percent active (expressed as acid) diethylenetriamine- pentamethylenephosphonic acid (DTPMP) solution one of the most efficient organic stabilizers known for the stabilization of peroxide, was added to achieve 0.05 percent DTPMP solution on O.D. pulp in bottle 1, 0.1 percent DTPMP solution on O.D. pulp in bottle 2, 0.25 percent DTPMP solution on O.D. pulp in bottle 3, and 0.35 percent DTPMP solution on O.D. pulp in bottle 4.
  • measured amounts of NaOH and hydrogen peroxide solutions were added to achieve 2.0 percent caustic and 2.0 percent peroxide (based on O.D. pulp) in each bottle.
  • the bleach liquor was added to the pulp in each of the four bags and the contents of each bag mixed thoroughly by kneading for 2 minutes.
  • the filtrate from the EDTA pretreatment step was added to achieve a targeted pulp consistency of 12 percent and then the contents were mixed thoroughly for 4 minutes .
  • the bag was sealed with minimum entrapped air and transferred to a 65 °C water bath for 1 hour. After the 1-hour bleaching interval, the pulp mixture was removed from the bath and promptly pressed to about 25 percent consistency.
  • the pulp pad was weighed and its exact consistency was determined. Based on the calculated consistency, the equivalent of 3 O.D. grams of the pulp pad was then used to form a handsheet according to TAPPI Test Method T 272. The handsheet reflectance was then measured using an ISO brightness meter.
  • Handsheet reflectance results are shown in Table 2 below, with Delta ISO Brightness representing the difference between the bleached handsheet versus the brightness of an unbleached handsheet:
  • the s-Me 2 DTTP is typically about 2 to 5 times as effective as DTPMP. The greater efficiency means less N and P is added to the bleaching process.
  • a mechanical pulp from a Northwestern U.S. paper mill was diluted to a consistency (based on O.D.) of 4 percent.
  • the pulp slurry was then treated with a 39 percent active NaEDTA aqueous solution (sold by The Dow Chemical Company under the trademark VERSENE 100 chelating agent) at a dosage of 0.5 percent based on the O.D. weight of the pulp at 65 °C for one hour.
  • the pulp was pressed to a consistency of about 25 percent, with the filtrate being saved for use as dilution water in a later step.
  • the pulp was then devided into 8 equal portions, each portion weighed into a plastic bag for bleaching with different bleach stabilizer systems. Respective bleaching steps were then performed as follows :
  • the filtrate from the EDTA pretreatment step was added to achieve a targeted pulp consistency of 12 percent and then the contents were mixed thoroughly for 4 minutes.
  • the bag was sealed with minimum entrapped air and transferred to a 65 °C water bath for 1 hour.
  • the pulp mixture was removed from the bath and a small portion of the bleach liquor was extracted for analysis of residual peroxide via starch-iodine thiosulfate titration.
  • the remaining pulp and liquor mixture was promptly pressed to about 25 percent consistency.
  • the pulp pad was weighed and its exact consistency was determined. Based on the calculated consistency, the equivalent of 3 O.D. grams of the pulp pad was then used to form a handsheet according to TAPPI Test Method T 272.
  • the handsheet reflectance was then measured using an ISO brightness meter.
  • N ⁇ , N ⁇ - dialkyl aminophosphonic acids of the present invention have unexpected and dramatically improved performance compared to the commercially available DTPMP product in peroxide bleaching of pulp.
  • the essentially pure s-Me 2 DTTP shows more than 2.5 times effectiveness over DTPMP from a delta brightness performance standpoint, and about 2.5 to 3 times more peroxide stabilization performance over DTPMP from a residual peroxide standpoint.
  • thermomechanical pulp from a Southern U.S. paper mill was diluted to a consistency (based on O.D. pulp) of 4 percent.
  • the pulp slurry was then treated with a 39 percent active Na 4 EDTA aqueous solution (sold by The Dow Chemical Company under the trademark VERSENE 100 chelating agent) at a dosage of 0.5 percent based on the O.D. weight of the pulp at 65 °C for one hour.
  • the pulp was pressed to a consistency of about 25 percent, with the filtrate being saved for use as dilution water in a later step.
  • the pulp was then divided into 8 equal portions, each portion weighed into a plastic bag for bleaching with different bleach stabilizer systems. Respective bleaching steps were then performed as follows :
  • bleach liquor was prepared in a separate bottle. Sufficient amount of 28 percent active diethylenetriaminepentamethylenephosphonic acid (DTPMP) solution was added to achieve 0.1 percent DTPMP solution on O.D. pulp in bottles 1 and 2, and 0.25 percent DTPMP solution on O.D. pulp in bottles 3 and 4. To each bottle, measured amounts of NaOH and hydrogen peroxide solutions were added to achieve 2.0 percent caustic and 2.0 percent peroxide (based on O.D. pulp) in each bottle. Immediately upon adding the peroxide portion of the bleach liquor and mixing the liquid, the bleach liquor was added to the pulp in each of the four bags and the contents of each bag mixed thoroughly by kneading for 2 minutes .
  • DTPMP active diethylenetriaminepentamethylenephosphonic acid
  • the filtrate from the EDTA pretreatment step was added to achieve a targeted pulp consistency of 12 percent and then the contents were mixed thoroughly for 4 minutes.
  • the bag was sealed with minimum entrapped air and transferred to a 65 °C water bath for 1 hour.
  • the pulp mixture was removed from the bath and a small portion of the bleach liquor was extracted for analysis of residual peroxide via starch- iodine thiosulfate titration.
  • the remaining pulp and liquor mixture was promptly pressed to about 25 percent consistency.
  • the pulp pad was weighed and its exact consistency was determined. Based on the calculated consistency, the equivalent of 3 O.D. grams of the pulp pad was then used to form a handsheet according to TAPPI Test Method T 272.
  • the handsheet reflectance was then measured using an ISO brightness meter.
  • Handsheet reflectance results are shown in Table 4 below, with Delta ISO Brightness representing the difference between the bleached handsheet versus the brightness of an unbleached handsheet:
  • N ,N ⁇ -dialkyl aminomethylenephosphonic acids of the invention For example, comparing the results of s-Me 2 DTTP (compound of the present invention) with those of comparative compound u-Me 2 DTTP, the importance of the N ⁇ ,N ⁇ -dialkyl structure is clearly illustrated.
  • Comparative compounds EDTMP, u-Me 2 EDDP, and s-Me 2 EDDP are all based on ethylenediamine. While compound s-Me 2 EDDP is symmetrically N-methylated, it does not perform to the high level of efficiency due to its insufficient structure. It is believed that the preferred N ⁇ ,N ⁇ -dialkyl aminomethylenephosphonic acid structures of the invention are active due to their superior metal ion control and ability to form catalytically active metal complexes .
  • the invention s-Me 2 DTTP N-oxide performs at least as well as the non-N oxide form.
  • the claimed N-oxide structures II and III thus suffer no performance drop due to their N-oxide substitution.
  • the compounds of the invention show an ability to out-perform the currently available products, even when applied at much lower dose rates.
  • the lower amounts of stabilizer required makes the compounds of the invention more preferred from an environmental standpoint.
  • the dramatically lower amounts of nitrogen (N) and phophorous (P) needed for adequate performance makes these products more attractive than the currently available products .

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Abstract

L'invention concerne des compositions comprenant au moins un acide N?α,Nφ¿-dialkyle aminométhylènephosphonique représenté par la formule (I) ou un N-oxyde associé de formule (II) ou (III), où R est un groupe alkylène comprenant entre 2 et 6 atomes de carbone, R¿1? et R2 sont chacun indépendamment un groupe alkyle comprenant entre 1 et 6, de préférence entre 1 et 4, atomes de carbone, un groupe hydroxyalkyle renfermant un alkyle comprenant entre 1 et 6, de préférence entre 1 et 4, atomes de carbone, ou un groupe carboxyalkyle renfermant un alkyle comprenant entre 1 et 6, de préférence entre 1 et 4, atomes de carbone, M est choisi, indépendamment dans chaque cas, dans le groupe constitué par H, NH4, une amine, un métal alcalin, un métal alcalino-terreux ou un groupe alkyle linéaire ou ramifié comprenant entre 1 et 4 atomes de carbone, et n est un nombre entier de 1 à 6. Etonnamment, on a découvert que ces compositions présentent un rendement supérieur en ce qui concerne le blanchiment au peroxyde de matières cellulosiques, l'inhibition de l'entartrage et de la corrosion ou l'élimination du tartre dans des applications relatives au traitement des eaux et aux champs pétrolifères, dans des applications de détergents et dans la chélation d'ions métalliques.
EP01930576A 2000-04-18 2001-04-18 Acides n-alpha ,n-omega -dialkyle aminomethylenephosphoniques et leur utilisation Withdrawn EP1276744A1 (fr)

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PCT/US2001/012660 WO2001079215A1 (fr) 2000-04-18 2001-04-18 Acides n?$g(a),n$g(v)¿-dialkyle aminomethylenephosphoniques et leur utilisation

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ITMI20021706A1 (it) * 2002-07-31 2004-02-01 Bozzetto Giovanni Spa Poliamminomeilenfosfono derivati.
ITMI20040162A1 (it) 2004-02-02 2004-05-02 Bozzetto Giovanni Spa Uso di polliaaminometilenfosfonati quali agenti disperdenti
EP2759518B1 (fr) * 2013-01-24 2019-05-22 MKS-DEVO Kimyevi Mad. San. Tic. A.S. Compositions de blanchiment à performances et stabilité améliorées et l'utilisation
US9023779B2 (en) 2013-03-15 2015-05-05 Ecolab Usa Inc. Inhibiting corrosion of aluminum on consumer ware washing product using phosphinosuccinic acid oligomers

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GB744633A (en) * 1952-06-06 1956-02-08 Dow Chemical Co N-alkyl-(or-aralkyl-) substituted alkylene polyamine methylene phosphonic acid compounds
US3470243A (en) * 1964-09-03 1969-09-30 Monsanto Co Tetrakis(dihydrogen phosphono methyl)-ethylene diamine,n,n'-dioxide and related compounds
GB1230172A (fr) * 1968-02-28 1971-04-28
GB1392044A (en) * 1971-06-26 1975-04-23 Ciba Geigy Ag Corrosion inhibiting composition
DE2360719A1 (de) * 1973-12-06 1975-06-12 Henkel & Cie Gmbh Pharmazeutische oder kosmetische praeparate
GB8414407D0 (en) * 1984-06-06 1984-07-11 Monsanto Europe Sa Detergent compositions
GB8826431D0 (en) * 1988-11-11 1988-12-14 Albright & Wilson Phosphate composition

Non-Patent Citations (2)

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Title
Mater. Struct.: 26,1993, page 425-431 *
See also references of WO0179215A1 *

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