+

WO1996033953A1 - Inhibiteurs du tartre et de la corrosion et agents d'elimination de taches - Google Patents

Inhibiteurs du tartre et de la corrosion et agents d'elimination de taches Download PDF

Info

Publication number
WO1996033953A1
WO1996033953A1 PCT/EP1996/001727 EP9601727W WO9633953A1 WO 1996033953 A1 WO1996033953 A1 WO 1996033953A1 EP 9601727 W EP9601727 W EP 9601727W WO 9633953 A1 WO9633953 A1 WO 9633953A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
polymer
corrosion
water
amine
Prior art date
Application number
PCT/EP1996/001727
Other languages
English (en)
Inventor
Keith Philip Davis
Euen Thomas Graham Gunn
Ajit Kumar
William John Nicholson
Original Assignee
Albright & Wilson Uk Limited
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
Priority claimed from GBGB9508433.1A external-priority patent/GB9508433D0/en
Priority claimed from GBGB9508432.3A external-priority patent/GB9508432D0/en
Priority claimed from GBGB9515486.0A external-priority patent/GB9515486D0/en
Priority claimed from GBGB9600736.4A external-priority patent/GB9600736D0/en
Priority claimed from GBGB9606156.9A external-priority patent/GB9606156D0/en
Application filed by Albright & Wilson Uk Limited filed Critical Albright & Wilson Uk Limited
Priority to AU57614/96A priority Critical patent/AU5761496A/en
Publication of WO1996033953A1 publication Critical patent/WO1996033953A1/fr

Links

Classifications

    • 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
    • C02F5/12—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 nitrogen
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/144—Aminocarboxylic acids

Definitions

  • This invention relates to corrosion and scale inhibitors for use in the treatment of aqueous systems, and to polymeric stain removers capable of removing, or reducing the intensity of, bleachable stains on fabrics, which do not depend upon available oxygen or on phosphonate groups.
  • a large number of compounds are known which inhibit corrosion of metals by water systems under various conditions and with varying degrees of effectiveness. They are frequently added to water used in evaporative or other cooling systems and central heating systems, as well as to process water, boiler water, water for hydrostatic testing of pipelines and water injected into or produced in oil wells to reduce corrosion of metal parts.
  • the most cost effective of these compounds can be used in concentrations typically in the range 1 to 1000 ppm.
  • a further problem in water treatment is inhibition of barium sulphate scale. This is encountered most commonly in oil wells, where the formation water contains high concentrations of barium and other alkaline earth metals. When sea water is injected into the formation to assist oil recovery, the resulting scale can block the pipe, and may even necessitate drilling a new well.
  • Existing scale inhibitors are inadequate to prevent costly problems at some severely affected locations. Such treatments are referred to as "squeeze treatments”.
  • Laundry detergents contain surfactants to remove fatty or other hydrophobic soil, usually builders to increase the cost effectiveness of the surfactant and usually fillers or diluents.
  • the surfactant could be present in amounts up to 90%, e.g. from 2 to 60% by weight but is usually within the range 10 to 40% by weight.
  • the builder, to be fully effective is required in amounts comparable to or greater than the surfactant, ideally about double the weight of surfactant.
  • the filler can be an inert solid such as sodium sulphate or a liquid medium such as water and is required to obtain a material having suitable physical properties to permit easy handling.
  • the filler usually constitutes up to 70% of the weight of the detergents.
  • laundry detergents require stain removers, usually in amounts of from 0.5 to 20% in order to be effective. They also usually contain various ancillary ingredients which are typically present in proportions less than 5% by weight each and less than 10% total.
  • Stains may be classified as "enzymatic" and "bleachable".
  • the former comprise the proteinaceous stains such as blood and egg and can be treated with enzymes such as protease while the latter comprise stains which are oxidisable by strong bleaches such as perborate.
  • Bleachable stains include tea, coffee, fruit juice and wine.
  • bleachable stains have been treated by including sodium perborate in the detergent formulation.
  • perborate and similar oxidising bleaches impossible or undesirable.
  • the oxidising bleaches cannot be included in most liquid detergents because they are chemically unstable in the presence of water, and they are too aggressive to be included in detergents designed for washing delicate and/or brightly coloured fabrics.
  • borates There are also environmental objections to the use of borates.
  • oxidising bleaches tend to inactivate any enzymes present and so inhibit the removal of enzymatic stains.
  • oxidising bleach is the use of phosphonates such as the methylene phosphonates of various amines. These are generally used instead of bleach in liquid detergents and often as an adjunct to bleach in powders. The method of action of phosphonates on bleachable stains has not hitherto been determined.
  • amido amines of the formula RCOHNCH 2 CH 2 NHCH 2 CH 2 OH (where R is a C 8 . 2 o alkyl or alkenyl Group) e.g. by hydrolysing the corresponding imidazoline
  • amphoacetate CH 2 COONa which is referred to as "amphoacetate".
  • Amphoacetate is widely used in cosmetics and toiletries because of its mildness.
  • sodium chloride which is formed as an unavoidable by-product of the above method of manufacture is often undesirable in the end formulation and this has seriously limited to the potential application of the surfactant.
  • Carboxy methyl amines such as ethylene diamine tetracetic acid and amino triacetic acid are notoriously corrosive towards metals.
  • corrosion inhibitors of our invention we include certain novel amine hydroxy succinates and hydroxy propionates which can be prepared by reacting epoxysuccinic or epoxyacrylic acids or their salts with amines.
  • the corrosion inhibitors of the present invention unlike conventional corrosion inhibitors, are not dependant on the presence of calcium to exert effective protection although they are tolerant of high levels of calcium. They are especially effective when the level of strong acid anions such as chloride and sulphate is relatively low, e.g. less than 150 ppm, especially less than 100 ppm. Soft water typically contains low levels of such anions. Conversely hard water usually contains relatively high levels of chloride and/or other strong acid anions.
  • polymer means a substance consisting of molecules characterised by the sequence of one or more types of monomer units .and comprising a simple weight majority of molecules containing at least 3 monomer units which are covalently bound to at least 1 other monomer unit or other reactant and consists of less than a simple weight majority of molecules of the same molecular weight. Such molecules are distributed over a range of molecular weights wherein differences in the molecular weight are primarily attributable to differences in the number of monomer units. In the context of this definition a "monomer unit” means the reacted form of a monomer in a polymer.
  • our invention provides a method of inhibiting corrosion of ferrous metals, by aqueous systems containing less than 150 mg chloride per litre which comprises adding to said systems a corrosion inhibiting amount of a carboxy amine corrosion inhibitor of the formula: R 2 NCHRCHRCOOH wherein each R is hydrogen, hydroxyl, amino or an organic group, provided that the total number of N linked [CHRCHRCOOH] groups equals or, preferably, exceeds the total number of amine hydrogen atoms; or a salt thereof.
  • the invention provides a method of inhibiting the corrosion of aluminium and its alloys in aqueous systems which comprises adding to said systems a corrosion inhibiting amount of a carboxy amine corrosion inhibitor of the formula R 2 NCHRCHRCOOM as hereinbefore defined.
  • our invention provides a composition for cleaning and disinfecting aluminium surfaces comprising a bacterocidally or bacterostatically effective amount of a disinfectant which tends to promote corrosion of aluminium and an amount of a corrosion inhibitor as aforesaid sufficient to inhibit said corrosion.
  • our invention provides a deicing composition comprising a corrosion inhibitor as aforesaid.
  • our invention provides a method of inhibiting scale formation in or around drill pipes in the presence of formation water containing barium salts, which comprises injecting a corrosion inhibitor as aforesaid into the formation.
  • the corrosion inhibitor is typically a compound of the above formula in which at least two R groups are organic groups.
  • the invention according to a second aspect provides a novel polymer composition for reducing the intensity of bleachable stains, which polymer has the formula
  • each R is hydrogen, methyl, ethyl, hydroxyethyl, hydroxy propyl,
  • each R is a mono or di-carboxy substituted ethyl group, optionally also substituted with a hydroxyl group e.g. a CHCOOM CHOHCOOM group, or hydrogen, provided that more than 50% and preferably all, of the R 1 groups are said substituted ethyl groups;
  • n has an average value between 2 and 10;
  • M is hydrogen or an alkali metal, alkaline earth metal or ammonium, or a base such that said polymer is water soluble;
  • the invention provides a laundry detergent composition comprising a surfactant, a builder and said novel polymer.
  • the invention further provides a method of treating bleachable stains which comprises applying said novel polymer or said laundry detergent thereto.
  • the invention also provides a composition
  • a composition comprising 2 to 60% by weight surfactant, 10 to 70% by weight builder, up to 70% by weight of a filler or diluent and 0.1 to 5% of said polymer.
  • the invention further provides a liquid detergent comprising surfactant, water, said polymer, and optionally a builder.
  • Our invention according to a third aspect provides a novel surfactant of the general formula :-
  • R is a C g to 25 alkyl or alkenyl group
  • R' is CO, CONHCH 2 CH 2 , CONCH 2 CH 2 CH 2 or (OCH 2 CH 2 ) a
  • R 2 is (CH 2 CH 2 O) b (CH,CH,N) c R 3 ; ' M
  • R 3 is [CHACHOHCOOX] or a C, to 4 alkyl or C 2 to 4 hydroxy alkyl group;
  • A is H or COOX;
  • X is hydrogen or an alkali metal, alkaline earth metal, ammonium or C, to 6 alkylammonium or alkanol ammonium;
  • n is 0 or 1 ;
  • a is 1 to 50;
  • b and c are each 0 to 50; na +b + c ⁇ 50 and, where b and c are both greater than O, the respective monomer units to which they are subscribed may be distributed either at random or in any order within the R 2 chain.
  • the corrosion inhibitor according to said first aspect of the invention may for example be an amino propionate, amino succinate, amino-2-hydroxy propionate or amino hydroxy succinate of the formula
  • R and R 1 are each organic groups and X is hydrogen or a salt forming cation, preferably forming a water soluble salt, such as an alkali metal, alkaline earth metal, ammonium or a C 1-4 mono, di or tri alkyl or alkanol ammonium group.
  • R in each of the above formulae may for example be: hydrogen; or a C 1-25 alkyl or C 2 . 25 alkenyl group; or a hydroxy substituted C 2 . 25 alkyl or alkenyl group; or an R 2 CONHR 3 group, wherein R 2 may be a C 1-25 alkyl or C 2 . 25 alkenyl group or a hydroxy substituted C 2 . 25 alkyl or alkenyl group and R 3 is a C 2 .
  • each R 4 group is independently selected from hydrogen, C,. 25 alkyl, C 2-25 alkenyl and hydroxy substituted C 2-25 alkyl or alkenyl groups R 3 has the same significance as before and x is 1 to 100; or an XOOCCH 2 group.
  • R contains from 1 to 25 preferably 2 to 20 carbon atoms total excluding any polymeric groups, which preferably contain an average of less than 20 monomer units.
  • R 1 may for example be any of the aforesaid R groups, but may additionally be an [R 3 O] n H group where n is 1 to 100 or a [NR 5 R 3 ] a [NR 4 R ] b R 6 group wherein R 5 is -CH 2 CH,COOX.
  • R 6 is any of the aforesaid R groups or an [R 3 O] n H group
  • a and n are each 1 to 100
  • b is 0 to 100 and, where b is greater than 0 the comonomers may be either randomly distributed or arranged in any order.
  • R- preferably has from 1 to 25 carbon atoms total, excluding any polymeric groups, which preferably contain less than 50 monomer units, more preferably less than 20 monomer units.
  • Preferred corrosion inhibitors for use according to our invention are epoxysuccinated or epoxyacrylated amines of the formula, R 5 (NR 5 CH 2 CH 2 ) a N(R 5 ) 2 where a is 3, 4,5 or 6, eg, pentaethylene hexamine hexakis (hydroxy succinic acid) and its salts.
  • a particularly preferred product is obtained by reacting epoxy succinic acid with a mixture comprising two or more amines of the afores-aid formula, either as a blend or as a mixed fraction, obtained by distillation over relatively broad temperature range.
  • Useful mixtures of compounds may also be obtained by reacting an epoxysuccinate with the relatively high molecular weight mixed homologues remaining after a reaction mixture used to prepare ethylene diamine has been distilled to separate out lower homologues.
  • epoxysuccinated, succinated or carboxyethylated derivatives of alkyl amido amines such as RCONH (CH 2 CH 2 NH) a CH 2 CH 2 A where R is preferably an alkyl or alkenyl group having 8 to 20 carbon atoms, A may be OH or NH 2 and a may be 1 to 30.
  • RCONH CH 2 CH 2 NH
  • A may be OH or NH 2
  • a may be 1 to 30.
  • Particularly preferred are the epoxysuccinated and the carboxythylated derivatives of the above compound wherein a is and A is OH. which may be obtained by hydrolysis of the hydroxyethyl imidazoline
  • the hydroxy succinated derivatives have been found to have value as a mild halogen free amphoteric surfactant and constitute a further aspect of the invention.
  • aminotris hydroxy succinic acid
  • glycine hydroxy succinic acid and its salts alkyl amine (especially fatty amine eg dodecylamine) hydroxy succinic acids and their salts
  • alkyl amine especially fatty amine eg dodecylamine
  • succinic acids and their salts aspartic acid hydroxy succinic acid and its salts
  • hexane 1 , 6 diamine bis (hydroxy succinic acid) and its salts and ethanolamine bis (hydroxy succinic acid) and its salts aminotris (hydroxy succinic acid) and its salts
  • alkyl amine especially fatty amine eg dodecylamine
  • the corrosion inhibitors of our invention are typically maintained at concentrations in the range 1 to 100 ppm in the water system to be treated, more usually 2 to 80 ppm, especially 5 to 50 ppm, more preferably 7 to 30 ppm eg 9 to 25 ppm.
  • the corrosion inhibitors are useful for preventing or inhibiting the corrosion of various metals including aluminium and its alloys and ferrous metals, for example, mild steel and are particularly effective in soft water, especially at neutral or acid pH, eg water containing less than 150 mg per litre chloride preferably less than 100 mg per litre and especially water having pH between 5 and 8 particularly 6.5 to 7.8 although the compounds may be used to treat water at pH as high as 9 or even 9.5. They are even effective in base exchange waters. We especially prefer water containing less than 150 mg per litre total of chloride and sulphate, e.g. less than 100 mg per litre.
  • the water contains less than 150 mg per litre total of strong mineral acid anions including chloride, sulphate, nitrate, phosphate and bromide.
  • strong mineral acid anions including chloride, sulphate, nitrate, phosphate and bromide.
  • Normally soft or moderately soft water, e.g. up to 150 mg per litre calcium hardness can be treated advantageously.
  • the corrosion inhibitor may be used in conjunction with other water treatment agents, including: scale inhibitors such as acetodiphosphonate, amino tris (methylene phosphonate), ethylenediamine tetrakis (methylenephosphonate), diethylenetriamine pentakis (methylenephosphonate), triethylenetetramine hexakis (methylenephosphonate) or higher members of the series of (n) ethylene (n + 1) amine (n + 3) (methyl enephosphonates), and/or polymaleic acid; one or more other corrosion inhibitors especially phosphono carboxylic acids such as phosphonosuccinic acid, 1 -phosphono- 1, 2,3 ,4-tetracarboxy butane and their higher teleomers, oxygen scavengers such as alkyl hydroxylamines; biocides such as quaternary phosphoniurn salts, eg tetrakis (hydroxymethyl) phosphonium salts, quaternary ammonium salts
  • De-icing compositions according to the invention typically contain either a concentrated, usually alkaline, aqueous solution of an organic electrolyte, such as sodium acetate, formate or propionate, or an aqueous water miscible organic liquid such as a di-or polyhydric alcohol or alcohol ether.
  • an organic electrolyte such as sodium acetate, formate or propionate
  • an aqueous water miscible organic liquid such as a di-or polyhydric alcohol or alcohol ether.
  • the pH is usually alkaline, e.g., 8 to 10.5 and the composition may contain minor amounts of water miscible organic solvents, polymeric thickeners, and surfactant wetting agents and an effective proportion of corrosion inhibitor, e.g. 5 to 500 ppm.
  • the latter type typically comprises 50 to 97% of an organic water miscible liquid such as ethylene or propylene glycol or other di- or polyhydric alcohol or alcohol ether.
  • the balance may comprise water, surfactant and/or polymer as well as an effective amount of corrosion inhibitor.
  • Corrosion inhibitors of our invention may be prepared by reacting an amine with a substantially equivalent amount, or small stoichiometric excess, of disodium or other alkali metal epoxysuccinate or epoxyacrylate in an aqueous alkaline medium.
  • the temperature is preferably maintained at an elevated level, eg, between 70 and 100°C preferably 80 to 98°C until the reaction is substantially complete. This usually takes over 10, eg 15 to 150 hours more usually 18 to 30 hours.
  • epoxysuccinate is prepared from hydrogen peroxide and maleic acid and is an intermediate in the preparation of tartaric acid. It is often contaminated with unreacted maleate and/or with tartrate.
  • maleate and tartrate should each be present in proportions of less than 10% preferably less than 5% especially less than 2.5% based on the weight of epoxysuccinate.
  • our invention provides a corrosion inhibiting pigment which is a solid composition which may be prepared by reacting a concentrated aqueous solution of any of the water soluble corrosion inhibitors according to the invention with a base or salt of calcium, zinc, barium, aluminium or other polyvalent metal and precipitating a solid salt according to any of the foregoing formulae (mutatis mutandis) wherein X represents a polyvalent metal.
  • our invention provides a corrosion inhibiting coating composition containing a pigment according to the invention.
  • the corrosion inhibiting pigment may be dissolved or dispersed in an anti-corrosive paint, varnish, enamel, lacquer, or other coating formulation.
  • the formulation may comprise a volatile liquid vehicle, such as water or a volatile organic solvent including petroleum spirit, tu ⁇ entine, ketones, esters and/or aromatic hydrocarbon solvent, and/or a drying oil, such as linseed oil, soya oil, rung oil or dehydrated castor oil, which may optionally be dissolved in said volatile organic solvent or emulsified in said water.
  • the formulation typically may also comprise a resin, eg a polyester, urea formaldehyde, melamine, acrylic, alkyd, polyurethane, vinyl chloride, vinyl acetate, phenolic or epoxy resin dissolved or dispersed therein and/or a dispersed pigment.
  • a resin eg a polyester, urea formaldehyde, melamine, acrylic, alkyd, polyurethane, vinyl chloride, vinyl acetate, phenolic or epoxy resin dissolved or dispersed therein and/or a dispersed pigment.
  • the pigment should be or should comprise other corrosion inhibiting pigments such as red lead, potassium zinc chromate, metallic zinc or aluminium powder or zinc oxide and/or that the formulation should contain one or more of the other corrosion inhibitors referred to above in addition to the corrosion inhibiting pigment of the invention.
  • the coating compositions may additionally contain any of the conventional paint ingredients, including pigments such as titanium oxide, iron oxide, carbon black, phthalocyanine pigments or aluminium stearate, chlorinated rubber, polystyrene, silicone, asphalt, wetting agents. dispersants, emulsifiers, biocides, flocculants. marine antifoulants. antifoams, viscosifiers, fire retardants, fluorescers, aerosol propellants, talc, clay and/or plasticisers.
  • pigments such as titanium oxide, iron oxide, carbon black, phthalocyanine pigments or aluminium stearate, chlorinated rubber, polystyrene, silicone, asphalt, wetting agents. dispersants, emulsifiers, biocides, flocculants. marine antifoulants. antifoams, viscosifiers, fire retardants, fluorescers, aerosol propellants, talc, clay and/or plasticisers.
  • the water soluble corrosion inhibitors of the invention may be used to provide a corrosion inhibiting treatment for metal surfaces such as steel, aluminium and aluminium alloys after any machining and prior to storage, coating, electroplating, polishing or etching.
  • metal surfaces such as steel, aluminium and aluminium alloys
  • the work is coated with an aqueous solution containing at least an operative amount of said corrosion inhibitor eg, 10 to 500 ppm preferably 25 to 300 eg 20 to 200 especially 25 to 100, more especially 30 to 80 ppm.
  • the work After contacting with the corrosion inhibiting solution the work may be rinsed and/or subjected to one or more coating or finishing operations such as resin coating, lacquering, enamelling, painting, electrophoretic coating, spattering, vapour deposition, electrodeposition, etching chemical or electrical polishing or may be put aside for storage.
  • coating or finishing operations such as resin coating, lacquering, enamelling, painting, electrophoretic coating, spattering, vapour deposition, electrodeposition, etching chemical or electrical polishing or may be put aside for storage.
  • the work may be greased for storage, but an advantage of the treatment is that greasing and hence subsequent degreasing may be avoided.
  • the liquid detergent of our invention preferably contains 5 to 50% e.g. 10 to 40% by weight surfactant, 5 to 60% e.g. 10 to 40% builder, 20 to 75% e.g. 40 to 70% by weight water and 0.1 to 2.5% of said polymer.
  • the liquid detergent preferably also contains conventional amounts of minor adjuncts including enzymes, soil suspenders such as sodium carboxymethyl cellulose, optical brighteners, dyes, perfumes, preservatives and foam modifiers.
  • the builder preferably comprises non-phosphate builders such as zeolite, carbonate, citrate, nitrilotriacetate and ethylene diamine tetracetate.
  • the stain remover is preferably a reaction product of epoxysuccinic acid or its salts with a mixture of amines, e.g. a polymeric mixture of amines with having four or more amine nitrogen atoms, especially amines of the formula NH 2 (CH 2 CH 2 NH) n H where n is greater than 2, e.g. 3 to 6.
  • the product typically has two or more 1, 2-dicarboxy-2-hydroxyethyl groups.
  • reaction products of from 3 to (n) molar proportions epoxysuccinic acid or its salts with mixtures of polyamines of the formula H[NHCH 2 CH 2 ] n NH 2 where (n) is the average value of n and lies between 4 and 6.
  • the individual amine components of the above mixture of polyamines may be separately reacted with epoxysuccinate and then mixed.
  • Polymers of our invention are preferably prepared by reacting a polymeric mixture of amines or its separate components with a substantially equivalent amount, or small stoichiometric excess, of disodium or other alkali metal epoxysuccinate in an aqueous alkaline medium.
  • the temperature is preferably maintained at an elevated level, e.g. between 70 to 100°C preferably 80 to 98°C until the reaction is substantially complete. This usually takes over 10, e.g. 15 to 150 hours, more usually 18 to 30 hours.
  • epoxysuccinate is prepared from hydrogen peroxide and maleic acid and is an intermediate in the preparation of tartaric acid. It is often contaminated with unreacted maleate and/or with tartrate.
  • maleate and tartrate should each be present in proportions of less than 10% preferably less than 5% especially less than 2.5% based on the weight of epoxysuccinate.
  • this level of purity is attainable by careful temperature control when preparing the epoxysuccinate maintaining the temperature sufficiently high to ensure substantially complete epoxidation of the maleate (e.g.
  • reaction with the amine may be carried out substantially in accordance with DE OS 2241 134 or US 5130052.
  • the detergent formulations of the invention may contain from 1% to 90% by weight of surfactant, more usually 2% to 70% e.g. 3% to 60% especially 4% to 50%, preferably 5% to 40%, more preferably 6% to 30%, most preferably 7% to 20%.
  • the surfactant may be, or may comprise, one or more anionic surfactants such as an alkyl benzene sulphate, alkyl sulphate, alkyl ether sulphate, paraffin sulphonate, olefin sulphonate, alkyl ether sulphonate, alkylphenyl sulphate, alkyl phenyl ether sulphate, alkyl sulphonsuccinate, alkyl sulphosuccinamate, alkyl isethionate, alkyl sarcosinate, soap, alkyl ether carboxylate, alkyl ether polycarboxylate, alkyl tauride, alkyl phosphate, alkyl ether phosphate or alkyl or thiol capped polyelectrolytes such as an alkylthiol capped polymaleic acid.
  • anionic surfactants such as an alkyl benzene sulphate, alkyl s
  • alkyl groups in this context refer to C8 to 22 straight or branched chain alkyl or alkenyl groups.
  • "Ether” refers to glyceryl, mono- or poly- ethyleneoxy, mono or poly propyleneoxy, or mixed ethyleneoxy/propyleneoxy, glyceryl/ethyleneoxy, glyceryl/propyleneoxy or glyceryl/ethyleneoxy/propyleneoxy.
  • the cation of the aforesaid anionic surfactants is usually sodium but may also be potassium or mono-, di-or tri-alkylolamine. Less commonly the cation may be lithium, ammonium, calcium, magnesium, zinc or a mono- di- or tri- alkyl amine such as isopropylamine or trimethylamine.
  • the surfactant may also be, or may comprise, one or more non-ionic surfactants such as the polyalkoxylated derivatives of alcohol's, carboxylic acids, alkyl phenols, alkylamines, alkanolamides. or glyceryl or sorbitan esters, wherein each compound has an "alkyl" group as hereinbefore defined, and the polyalkylene oxy group comprises from 1 to 50 ethyleneoxy and/or propyleneoxy groups.
  • non-ionic surfactants such as the polyalkoxylated derivatives of alcohol's, carboxylic acids, alkyl phenols, alkylamines, alkanolamides. or glyceryl or sorbitan esters, wherein each compound has an "alkyl" group as hereinbefore defined, and the polyalkylene oxy group comprises from 1 to 50 ethyleneoxy and/or propyleneoxy groups.
  • the non-ionic surfactant may be an alkanolamide, e.g. a mono- or di-alkanolamide, a lactobionamide, an alkylpolyglycoside or an amine oxide, or an alkyl or thiol capped polyvinyl alcohol or polyvinylpyrrolidone, or a sugar ester.
  • an alkanolamide e.g. a mono- or di-alkanolamide, a lactobionamide, an alkylpolyglycoside or an amine oxide, or an alkyl or thiol capped polyvinyl alcohol or polyvinylpyrrolidone, or a sugar ester.
  • the surfactant may be, or may comprise, one or more amphoteric surfactants such as a betaine or sulphobetaine, and/or one or more cationic surfactants such as an alkyl trimethyl ammonium, alkyl pyridinium, alkyl dimethylbenzylammonium, alkyl isoquinolinium. alkyl imidazoline or alkylamido amine.
  • the counter ion of the cationic surfactant may typically be chloride, methosulphate, formate, acetate, citrate, lactate, tartrate or bromide.
  • mixtures of anionic and/or non-ionic surfactants with amphoteric surfactants are also favoured, as are mixtures of cationic with amphoteric surfactants, with or without non-ionics. Mixtures of anionic with cationic surfactants are not normally favoured.
  • the detergent composition may contain a total of up 90% by weight of builder. Most commonly the detergent formulation contains from 1% to 80% builder, e.g. 5% to 75%, more usually 10% to 70% preferably 15% to 60%, more preferably 20% to 50%, most preferably 25% to 40% by weight based on the total weight of the composition.
  • the builder may be any substances that assists the action of the surfactant by ameliorating the effects of calcium in the wash liquor and/or maintaining alkalinity in the wash.
  • the builder could for example, be or comprise, an alkali metal orthophosphate or condensed phosphate, especially sodium tripolyphosphate, tetrasodium or tetrapotassium pyrophosphate or sodium tetraphosphate, or a phosphonate.
  • the builder is a non-phopshate builder such as zeolite, citrate, ethylenediamine tetracetate. nitrilotriacetate. silicate or carbonate.
  • the detergent compositions of this invention usually contain a filler or diluent which is typically sodium sulphate, in proportions up to 80%, more usually 10 to 60% by weight. Liquid detergents containing water as diluent are also provided.
  • detergent formulations of this invention may optionally contain any of the detergent ancillary ingredients.
  • detergent ancillary ingredients will be used herein to include all those ingredients, other than surfactant, polymeric stain remover, builder and any filler or diluent, which have been or may be used to enhance the performance, appearance, pourability, stability, fragrance or ease of use of detergent compositions.
  • the term includes, for instance, soil suspending agents such as sodium carboxymethyl cellulose, optical brighteners, photoactive bleaches, sequestrants, buffers, foaming agents, foam stabilisers, antifoams, preservatives, biocides, enzymes, enzyme stabilisers, hydrotropes, polymers, dyes, vegetable oils, mineral oils, pigments, fragrances, abrasives, perfume enhancers and fabric conditioners, including cationic fabric conditioners and inorganic fabric conditioners such as bentonite.
  • soil suspending agents such as sodium carboxymethyl cellulose, optical brighteners, photoactive bleaches, sequestrants, buffers, foaming agents, foam stabilisers, antifoams, preservatives, biocides, enzymes, enzyme stabilisers, hydrotropes, polymers, dyes, vegetable oils, mineral oils, pigments, fragrances, abrasives, perfume enhancers and fabric conditioners, including cationic fabric conditioners and inorganic fabric conditioners such as bentonite
  • compositions of the invention preferably contain soil suspending agents such as sodium carboxymethyl cellulose typically in proportions of from 0.01% to 3% by weight based on the weight of the composition, especially 0.1% to 2% e.g. 0.5% to 1.5%.
  • soil suspending agents such as sodium carboxymethyl cellulose typically in proportions of from 0.01% to 3% by weight based on the weight of the composition, especially 0.1% to 2% e.g. 0.5% to 1.5%.
  • the compositions typically contain fragrances, dyes, pigments and/or preservatives in a total proportion of from 0.1% to 5% by weight, e.g. 0.2% to 3% by weight based on the total weight of the composition.
  • the polymers of the invention may be used in conjunction with oxidising bleach, in the presence of which they tend to inhibit the loss of available oxygen from the formulation during storage. They, however, are more commonly used in bleach-free formulations.
  • the compositions of the invention may also comprise conventional amounts of bleach activators such as tetracetylethylenediamme.
  • the formulation may also contain foam control agents such as silicone antifoams and/or mineral oils where the compositions are intended for use in front loading washing machines, or foam boosters where the products are intended for hand washing or use in top loading washing machines.
  • Detergent ancillary ingredients are normally present in a total concentration below 10% by weight based on the total composition.
  • the polymers of the invention in addition to acting as stain removers and bleach stabilisers also reduce the corrosion of steel or aluminium trim on washing machines.
  • Pentaethylene hexamine was epoxysuccinated as follows:
  • Di-sodium epoxy succinate (20g, 0.114m) referred to hereinafter as "DSES” was dissolved in water (30g, 0.6m) by gentle heating at 40°C. This was followed by the addition of pentaethylene hexamine (4.4g, 0.019m). The temperature was then raised to 95°C to give a clear pale yellow solution. Heating and stirring was then continued for a further 8 hours. The reaction was monitored by 1H-NMR (in D 2 O) for the disappearance of DSES peak at 3.6ppm.
  • the final solution is clear, light yellow with a solid concentration of 44.9%.
  • Epoxysuccinated amido amine was prepared as follows:
  • the product was diluted to 35% by weight solids.
  • a sample diluted to 10% by weight solids had a pH of 10.1.
  • Carboxyethylated amido amine was prepared as follows:
  • Di sodium epoxy succinate (17.6g, 0.1m) was dissolved in water (eg, 1.57m) at room temperature with stirring. This was followed by the addition of "Polyamine” B, a polyethylene polyamine still residue comprising a mixture of higher polyethylene polyamines (5g, 0.1m). The mixture was then heated at 90-95°C for 20 hours to give a clear solution. pH mixture remained at 13 throughout reaction. Ratio of DSES to amine (NH's) was 1 :1.
  • Berolamine is a trademark of Berol Nobel.
  • Di sodium epoxy succinate (20g, 0.114m) was dissolved in distilled water (30g, 1.67m) with stirring at room temperature. This was followed by the addition of pentaethylene hexamine (6.6g, 0.028m) to give a pale yellow solution (clear). This was heated at 95-100°C for 20 hours. pH of solution remained at 13 throughout reaction. Ratio of DSES to amine was 4:1.
  • Delta-gluconolactone (7.5g, 0.042m) was dissolved in methanol (150g, 4.69m) by refluxing over 45mins. Pentaethylene hexamine (4.9g, 0.021m) was then added in one portion and reaction mixture was then heated for a further 30 min, with stirring. The light yellow coloured solution was then evaporated under reduced pressure to give a white foam.
  • Di-sodium epoxy succinate (176g, lm) is added to polyethylene polyamine (lm, based on NH groups). This is followed by the addition of water to give a 50% w/w solution. The mixture is then stirred and heated at 95°C for 8 hours to give a clear pale yellow solution.
  • Example 13 Di-sodium epoxy succinate (176g, lm) is added to polyethylene polyamine (lm, based on NH groups). This is followed by the addition of water to give a 50% w/w solution. The mixture is then stirred and heated at 95°C for 8 hours to give a clear pale yellow solution.
  • Di sodium epoxy succinate (lOg, 0.057m) was dissolved in distilled water (20g. 1.1 1m) with stirring at 45°C. This was followed by the addition of DL-glutamic acid (4.7g, 0.029m). The mixture was then heated at 90-95°C for 20 hours to give a clear solution. However, on cooling to room temperature some crystals dropped out, these are currently been analysed. pH of reaction throughout was 13. Ratio of DSES to amino acid was 1 :1.
  • Di sodium epoxy succinate (20g, 0.114m) was dissolved in distilled water (30g, 1.67m) with stirring at 45°C. This was followed by the addition of triethylenetetramine (4.16g, 0.028m) to give a clear light pale yellow solution. The mixture was then heated at 90-95°C for 18 hours, to give a clear pale yellow solution. pH of reaction throughout remained at 13. Ratio of DSES to amine was 4:1.
  • Di sodium epoxy succinate (15g, 0.085m) was dissolved in distilled water (22.5g. 1.25m) with stirring at 45°C. This was followed by the addition of diethylenetriamine (2.93g. 0.028m) to give a thick white suspension, which went clear after 1 hour. The mixture was then heated at 90-95°C for 18 hours, to give a clear light yellow solution. pH of reaction throughout remained at 13. Ratio for DSES to amine was 3:1.
  • Di sodium epoxy succinate (20g, 0.114m) was dissolved in distilled water (30g, 1.67m) with stirring at 45°C. This was followed by the addition of tetraethylenepentamine (4.3g, 0.023m) to give a clear light yellow solution. The mixture was then heated at 90-95°C for 18 hours, to give a clear pale yellow solution. pH of reaction throughout remained a tl3. Ratio for DSES to amine was 5:1.
  • Di-sodium epoxy succinate 35.79g, 0.203m was dissolved in water (55g, 3.1m) by gentle heating at 40°C. This was followed by the addition of pentaethylene hexamine (3.97g, 0.017m), tetraethylene pentamine (3.24g, 0.017m) and triethylene tetramine (0.56g, 0.0038m). The temperature was then raised to 95°C to give a clear pale yellow solution. Heating and stirring was then continued for a further 8 hours. The reaction was monitored by 1H-NMR (in D 2 O) for the disappearance of DSES peak at 3.6ppm.
  • 2-bromo-2-nitropropane-l,3-diol(BNP) is manufactured and marketed as an antimicrobial agent for industrial use. It is known to be aggressive towards aluminium, which is of concern as one use for the product is in aircraft toilet cleaning formulations.
  • Coupon tests were performed on a typical aluminium alloy to determine whether .amine hydroxysuccinate derivatives, could inhibit corrosion by a 5% w/v BNP solution in synthetic tap water at pH 4.5
  • Corrosion rates are expressed in mils/year using 5% by weight BHP and various concentrations (A) of the product of Example 18 and (B) the product of Example 2 on alloy type 2024.
  • a de-icer composition comprises water and 60% by weight of sodium acetate adjusted to a pH of 9.5, together with 0.5% of a surfactant mixture comprising, by weight, 3 parts alkyl benzene sulphonate and 1 part C 12 . M alkyl 3 mol ethoxylate. The composition has been observed to cause pitting of aluminium surfaces.
  • Example 18 To the above composition is added 50 ppm of the product of Example 18. The incidence of corrosion is substantially reduced.
  • a de-icer composition consists of ethylene glycol, 3% by weight water, 1% by weight of a polymaleate and 1% by weight of C I2 . ]4 alkyl 2 mole ethoxylate. Addition of 50 ppm of the product of Example 18 substantially reduced corrosion of the formulation towards aluminium surfaces.
  • Example 18 To illustrate calcium tolerance in the absence of chloride a synthetic hardwater was prepared containing 1000 ppm calcium hardness as calcium acetate. The product of Example 18 gave excellent corrosion inhibition and showed good stability with no evidence of precipitation.
  • a polymeric mixture of alkylene amines comprising pentaethylene hexamine, tetraethylene pentamine and triethylene tetramine was reacted with epoxysuccinate as follows :-
  • Di-sodium epoxy succinate (1330.9g, 8.56m) was dissolved in water (1730.9g, 96.2m) by gentle heating at 40°C. 2. 400gms of a mixture of pentaethylene hexamine (47.1 % by weight), tetraethylene pentamine (44.2% by weight) triethylene tetramine (8.3% by weight) and diethylene triamine (0.4% by weight) was added.
  • Oil heater circulator was then set at 95°C and stirring continued.
  • the final solution was a clear, amber coloured solution, with solids concentration being 50%.
  • EXAMPLE 27 A BUILT LIQUID DETERGENT COMPOSITION COMPRISING POLYMERIC STATN REMOVER
  • composition was prepared, all weights being expressed as the percentage of active ingredient by weight, based on the total weight of the composition :-
  • the stain removal ability of the polymeric stain remover of Example 26 was determined according to the method given below. As a standard, the stain remover was omitted from the composition of Example 2.
  • Example 2 The performance of Example 2 and of the standard on bleachable stains was tested on each of the following four types of test cloths:-
  • the ⁇ MP114' cloth is a pre-stained cotton cloth supplied by the 'Swiss Federal Laboratories for materials testing and research - Switzerland' and is recognised as a standard test cloth in the detergent industry. Tea, coffee and blackcurrant juice test cloths were prepared in-house, by manual staining of cloth. The test fabrics are measured for reflectance values before and after laundering. 2. Four 3 inch square pieces of each standard pre-stained cloth (see above) were placed into a Micle, Novotronic W820 automatic washing machine, set for short programme cotton wash at 60°C.
  • test cloths were washed together at 60°C in the washing machine, with 1 OOmls (10 grams per litre of wash water) of the detergent sample.
  • the water used was of an approximate water hardness of 200 parts per million of calcium carbonate. After the washing cycle the test cloths were rinsed in water of the same hardness.
  • W is the reflectance reading of the laundered fabric.
  • W 2 is the reflectance reading of stained fabric.
  • W is the reflectance reading of unstained fabric of the same type.
  • the respective actual % stain removal for Example 27 and the standard is given below in

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Detergent Compositions (AREA)

Abstract

Des produits obtenus par réaction entre des agents de carboxylation, tels que l'acide époxysuccinique, et des amines comprenant une pluralité d'atomes d'azote, telles que des polyamines de polyéthylène, constituent des inhibiteurs de corrosion possédant une efficacité particulière dans le traitement de l'eau douce, ainsi que des agents d'élimination de taches, notamment des agents polymères utiles dans les détergents.
PCT/EP1996/001727 1995-04-26 1996-04-25 Inhibiteurs du tartre et de la corrosion et agents d'elimination de taches WO1996033953A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU57614/96A AU5761496A (en) 1995-04-26 1996-04-25 Stain corrosion and scale inhibitors

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
GB9508433.1 1995-04-26
GBGB9508433.1A GB9508433D0 (en) 1995-04-26 1995-04-26 Novel surfactants
GB9508432.3 1995-04-26
GBGB9508432.3A GB9508432D0 (en) 1995-04-26 1995-04-26 Corrosion inhibitors
GBGB9515486.0A GB9515486D0 (en) 1995-07-28 1995-07-28 Stain removal
GB9515486.0 1995-07-28
GBGB9600736.4A GB9600736D0 (en) 1996-01-16 1996-01-16 Corrosion and scale inhibitors
GB9600736.4 1996-01-16
GB9606156.9 1996-03-23
GBGB9606156.9A GB9606156D0 (en) 1996-03-23 1996-03-23 Polymeric stain remover

Publications (1)

Publication Number Publication Date
WO1996033953A1 true WO1996033953A1 (fr) 1996-10-31

Family

ID=27517288

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/001727 WO1996033953A1 (fr) 1995-04-26 1996-04-25 Inhibiteurs du tartre et de la corrosion et agents d'elimination de taches

Country Status (2)

Country Link
AU (1) AU5761496A (fr)
WO (1) WO1996033953A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008045677A1 (fr) * 2006-10-13 2008-04-17 Cytec Technology Corp Inhibiteurs de calamine à base de polyamines à modification hydrophobe
US7999065B2 (en) 2006-10-13 2011-08-16 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
WO2012063055A1 (fr) * 2010-11-09 2012-05-18 Champion Technologies Ltd Procédé et composition empêchant la corrosion de surfaces métalliques
AU2011226768B2 (en) * 2006-10-13 2012-12-20 Cytec Technology Corp Hydrophobically modified polyamine scale inhibitors
US9290851B2 (en) 2014-06-03 2016-03-22 Ecolab Usa Inc. Specific 3-alkylamino-2-hydroxysuccinic acids and their salts as corrosion inhibitors for ferrous metals
WO2018099624A1 (fr) 2016-12-01 2018-06-07 Clariant International Ltd Utilisation d'une composition contenant au moins un composé de sucre-amide biodégradable en combinaison avec au moins un synergiste à base de soufre pour l'inhibition de la corrosion d'un équipement métallique dans des applications de champ pétrolifère

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2072504A5 (fr) * 1969-12-01 1971-09-24 Henkel & Cie Gmbh
FR2196993A1 (fr) * 1972-08-22 1974-03-22 Hoechst Ag
WO1991012354A1 (fr) * 1990-02-06 1991-08-22 Monsanto Company Compositions et procede d'inhibition de la corrosion de metaux ferreux
EP0509382A2 (fr) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Stabilisateurs de blanchiment biodégradables pour détergents
EP0513948A2 (fr) * 1991-05-15 1992-11-19 Hampshire Chemical Corporation Compositions de nettoyage pour surfaces dures contenant des agents de chelation biodégradable
EP0520761A2 (fr) * 1991-06-28 1992-12-30 Exxon Chemical Patents Inc. Inhibiteurs de corrosion à base de produits d'addition d'amines

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2072504A5 (fr) * 1969-12-01 1971-09-24 Henkel & Cie Gmbh
FR2196993A1 (fr) * 1972-08-22 1974-03-22 Hoechst Ag
WO1991012354A1 (fr) * 1990-02-06 1991-08-22 Monsanto Company Compositions et procede d'inhibition de la corrosion de metaux ferreux
EP0509382A2 (fr) * 1991-04-17 1992-10-21 Hampshire Chemical Corporation Stabilisateurs de blanchiment biodégradables pour détergents
EP0513948A2 (fr) * 1991-05-15 1992-11-19 Hampshire Chemical Corporation Compositions de nettoyage pour surfaces dures contenant des agents de chelation biodégradable
EP0520761A2 (fr) * 1991-06-28 1992-12-30 Exxon Chemical Patents Inc. Inhibiteurs de corrosion à base de produits d'addition d'amines

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012241116B2 (en) * 2006-10-13 2013-06-13 Cytec Technology Corp Hydrophobically modified polyamine scale inhibitors
RU2576616C2 (ru) * 2006-10-13 2016-03-10 Сайтек Текнолоджи Корп Гидрофобно модифицированные полиаминовые ингибиторы образования накипи
AU2007307999B2 (en) * 2006-10-13 2011-10-20 Cytec Technology Corp Hydrophobically modified polyamine scale inhibitors
US10144663B2 (en) 2006-10-13 2018-12-04 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
RU2455318C2 (ru) * 2006-10-13 2012-07-10 Сайтек Текнолоджи Корп Гидрофобно модифицированные полиаминовые ингибиторы образования накипи
AP2510A (en) * 2006-10-13 2012-11-21 Cytec Tech Corp Hydrophobically modified polyamine scale inhibitors
AU2011226768B2 (en) * 2006-10-13 2012-12-20 Cytec Technology Corp Hydrophobically modified polyamine scale inhibitors
CN101522571B (zh) * 2006-10-13 2013-01-09 氰特技术公司 疏水性修饰的聚胺污垢抑制剂
US8450452B2 (en) 2006-10-13 2013-05-28 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
EP2366669A3 (fr) * 2006-10-13 2018-01-10 Cytec Technology Corp. Inhibiteurs d'échelle de polyamine hydrophobiquement modifiés
US7999065B2 (en) 2006-10-13 2011-08-16 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
US9745216B2 (en) 2006-10-13 2017-08-29 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
WO2008045677A1 (fr) * 2006-10-13 2008-04-17 Cytec Technology Corp Inhibiteurs de calamine à base de polyamines à modification hydrophobe
US9365442B2 (en) 2006-10-13 2016-06-14 Cytec Technology Corp. Hydrophobically modified polyamine scale inhibitors
RU2621705C2 (ru) * 2006-10-13 2017-06-07 Сайтек Текнолоджи Корп Гидрофобно модифицированные полиаминовые ингибиторы образования накипи
AU2011327873A1 (en) * 2010-11-09 2013-05-30 Champion Technologies Ltd Method and composition for preventing corrosion of metal surfaces
AU2011327873C1 (en) * 2010-11-09 2018-02-08 Champion Technologies Ltd Method and composition for preventing corrosion of metal surfaces
US10000641B2 (en) 2010-11-09 2018-06-19 Ecolab Usa Inc. Method and composition for preventing corrosion of metal surfaces
WO2012063055A1 (fr) * 2010-11-09 2012-05-18 Champion Technologies Ltd Procédé et composition empêchant la corrosion de surfaces métalliques
US9290851B2 (en) 2014-06-03 2016-03-22 Ecolab Usa Inc. Specific 3-alkylamino-2-hydroxysuccinic acids and their salts as corrosion inhibitors for ferrous metals
WO2018099624A1 (fr) 2016-12-01 2018-06-07 Clariant International Ltd Utilisation d'une composition contenant au moins un composé de sucre-amide biodégradable en combinaison avec au moins un synergiste à base de soufre pour l'inhibition de la corrosion d'un équipement métallique dans des applications de champ pétrolifère

Also Published As

Publication number Publication date
AU5761496A (en) 1996-11-18

Similar Documents

Publication Publication Date Title
US6071434A (en) Phosphino derivatives
EP1254144B2 (fr) Composes phosphores
US5606105A (en) Water treatment agent
US3776850A (en) Detergent formulations
US3398198A (en) Less than fully propylated (beta hydroxy propyl) ethylene diamine and method of preparation thereof
EP0666305B1 (fr) Compositions de nettoyage acides
CA2182677C (fr) Compositions de nettoyage acides
US5733859A (en) Maleic acid-based aqueous cleaning compositions and methods of using same
AU701869B2 (en) Limescale removing compositions
WO1996033953A1 (fr) Inhibiteurs du tartre et de la corrosion et agents d'elimination de taches
US5672578A (en) Limescale removing compositions
AU2009207668A1 (en) Surface treatment composition containing phosphonic acid compounds
EP1668064B1 (fr) Nouveaux polymeres
US3784486A (en) Alpha,alpha-carboxyalkoxy succinic acid compounds as detergent builders and sequestering agents
EP1791893B1 (fr) Polymères d'aminophosphinate
JP3441853B2 (ja) 液体漂白剤組成物
US5726341A (en) Amine nitrile intermediate for the preparation of 2-hydroxyethyl iminodiacetic acid
US4107064A (en) Metal sequestering method
US4066687A (en) 2,3-carboxy alkoxy succinic acid and salts thereof
EP3861093A1 (fr) Polymère détergent et composition détergente
US3980578A (en) Metal sequestering method and composition using α,α'-carboxyalkoxy succinic acid compounds
AU708209B2 (en) Maleic acid-based aqueous cleaning compositions and methods of using same
JPS59179681A (ja) 金属イオン封鎖剤
WO1996030334A1 (fr) Intermediaire aminonitrile destine a la preparation de l'acide 2-hydroxypropyle iminodiacetique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AU BB BG BR CA CN CZ EE GE HU IS JP KG KP KR LK LR LT LV MD MG MK MN MX NO NZ PL RO SG SI SK TR TT UA UG US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载