CA2055238A1 - Corrosion inhibition - Google Patents
Corrosion inhibitionInfo
- Publication number
- CA2055238A1 CA2055238A1 CA002055238A CA2055238A CA2055238A1 CA 2055238 A1 CA2055238 A1 CA 2055238A1 CA 002055238 A CA002055238 A CA 002055238A CA 2055238 A CA2055238 A CA 2055238A CA 2055238 A1 CA2055238 A1 CA 2055238A1
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- CA
- Canada
- Prior art keywords
- aqueous
- systems
- formula
- agents
- compound
- 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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Classifications
-
- 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
- C23F11/173—Macromolecular compounds
Abstract
Abstract of the Disclosure Corrosion Inhibition A method of inhibiting corrosion of metal surfaces in contact with an aqueous system, comprising contacting the metal surfaces with a telomer compound having the formula I:
I
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical; and n is an average integer ranging from 1 to 60.
I
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical; and n is an average integer ranging from 1 to 60.
Description
20~3238 The pre~sent invention relates to a method of inhibiting corrosion of metal surfaces in contact with an aqueous system.
In U.S. Patent Specification No: 4046707 there is described a method of inhibiting the precipitation of scale-forrning salts of calcium, magnesium, barium and strontium from aqueous systems. The method comprises adding to the aqueous system a minor proportion of a product comprising a telomeric compound of formula:
o R" R"
Il I _ R--p _--CH2 C----CH2CH CO2H
and salts thereof, in which R" is hydrogen, methyl or ethyl; R is hydrogen, Cl~Cl8 alkyl, Cs-CI2 cycloalkyl, aryl, aralkyl, a residue of formula R" R"
I _ in which R" has its previous significance and the sum of m and n is an integer of at most 100, or R is a residue -OX in which X is hydrogen or Cl-C4 alkyl; and Rl is a residue - OX
in which X has its previous significance.
There is no suggestion in U.S. Patent Specification No: 4046707 that any of the disclosed telomers could have any inherent corrosion - inhibiting properties. In fact, many of the disclosed telomers exhibit no or minimal corrosion - inhibiting properties.
In U.S. Patent Speci~lcation No: 4239648 there are described compositions, useful for inhibiting the corrosion of ferrous metals, in contact with aqueous systems, comprising a) , .
:~ . . : , . . . . .
.. . .- .. . - ~ .
. .: . . .: . :
... , . , :
.
In U.S. Patent Specification No: 4046707 there is described a method of inhibiting the precipitation of scale-forrning salts of calcium, magnesium, barium and strontium from aqueous systems. The method comprises adding to the aqueous system a minor proportion of a product comprising a telomeric compound of formula:
o R" R"
Il I _ R--p _--CH2 C----CH2CH CO2H
and salts thereof, in which R" is hydrogen, methyl or ethyl; R is hydrogen, Cl~Cl8 alkyl, Cs-CI2 cycloalkyl, aryl, aralkyl, a residue of formula R" R"
I _ in which R" has its previous significance and the sum of m and n is an integer of at most 100, or R is a residue -OX in which X is hydrogen or Cl-C4 alkyl; and Rl is a residue - OX
in which X has its previous significance.
There is no suggestion in U.S. Patent Specification No: 4046707 that any of the disclosed telomers could have any inherent corrosion - inhibiting properties. In fact, many of the disclosed telomers exhibit no or minimal corrosion - inhibiting properties.
In U.S. Patent Speci~lcation No: 4239648 there are described compositions, useful for inhibiting the corrosion of ferrous metals, in contact with aqueous systems, comprising a) , .
:~ . . : , . . . . .
.. . .- .. . - ~ .
. .: . . .: . :
... , . , :
.
- 2 ~ 2 3 8 the telomeric compounds used in the method of U.S. Patent No: 4046707 and b) one or more compounds selected from i) a zinc salt, ii) a polyphosphate, iii) a silicate and/or iv) a molybdate.
The telomers preferred for use in the compositions of U.S. Patent Specification No:
4239648 are those having the formula O R" R"
Il I
H P--CH2 C --CH2CH CO2H or I m R"
HO2C CH CH2 P 1 CH2 ~--~ CH2CH CO2H
OX CO2H m in which R", X and m have their previous significance.
These preferred telomers, when used alone at a level of 100 ppm in the Aerated Solution Bottle Test, give a percentage level of corrosion inhibition of at most, only 43%. Only when those preferred telomers were used in conjunction with a zinc, polyphosphate silicate or molybdate coadditive, did the combinations so obtained attain satisfactory corrosion inhibition levels of 80% or more.
We have now found sulprisingly, that by selecting certain telomers, distinct from those preferred in 4239648, out of the broad range of telomers disclosed in U.S. 4046707, the selected telomers have inherently high corrosion inhibiting properties, without the need for co-additives to boost their corrosion inhibiting effect.
Accordingly, the present invention provides a method of inhibiting corrosion of metal surfaces in contact with an aqueous system by contacting the metal surfaces with a telomer compound having the formula I:
205a2~8 O H
MO ~ 1 CH2--C ~ H
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical; and n is an average integer ranging from 1 to 60, preferably from4~o30.
Alkali metal cations M are, principally, lithium, sodium and potassium ions; alkaline earth metal atoms are, e.g., calcium, magnesium, barium or strontium; ammonium ions include, e.g. trimethylammonium, triethylammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium and bis(2-hydroxyethyl)-2-(hydroxy-3-p-nonylphenoxypropyl) ammonium ions; and quaternised amine radicals include those having the formula N~3(RaRbRCRd)4 An~3 in which Ra~ Rh, Rc and Rd are the same or different, and each is Cl-C6 alkyl, especially methyl or ethyl, or each is 2-hydroxyethyl, or one of Ra~ Rb, Rc and Rd is benzyl, and the other three of Ra~ Rb Rc and Rd are Cl-C6 alkyl, especially methyl or ethyl, and An(3 is a halide ion, especially chloride or bromide, hydroxyl or sulphate.
The compounds of formula I are known compounds, having been broadly described in US
Patent 2957~31 and, of course, in US Patent 4046707.
The compounds of formula I may be produced by reacting the appropriate molar ratio of acrylic acid, or a Cl-C6 aLkyl ester thereof, depending upon the desired value of n, with one mole of a di(CI-C4 alkyl)phosphite or diarylphosphite, in particular diethylphosphite.
The reaction may be conveniently conducted in the presence of a polymerization initiator such as bisazoisobutyronitrile; organic peroxides such as benzoyl peroxide, methylethylketone peroxide, di-tertiarybutyl peroxide and mono-butyl hydroperoxide; or oxidizing agents such as hydrogen peroxide, sodium perborate or sodium persulphate.
At completion of the reaction between diethyl phosphite and the acrylic monomer, the crude reaction mixture may be purified, if desired, by conventional techniques, for example, any excess diethyl phosphite reactant may be removed by distillation of the . " ~
: .
.,, . ~; .' -~ ' ., . . , , , ~
.. , , . ~ - -~. ..
The telomers preferred for use in the compositions of U.S. Patent Specification No:
4239648 are those having the formula O R" R"
Il I
H P--CH2 C --CH2CH CO2H or I m R"
HO2C CH CH2 P 1 CH2 ~--~ CH2CH CO2H
OX CO2H m in which R", X and m have their previous significance.
These preferred telomers, when used alone at a level of 100 ppm in the Aerated Solution Bottle Test, give a percentage level of corrosion inhibition of at most, only 43%. Only when those preferred telomers were used in conjunction with a zinc, polyphosphate silicate or molybdate coadditive, did the combinations so obtained attain satisfactory corrosion inhibition levels of 80% or more.
We have now found sulprisingly, that by selecting certain telomers, distinct from those preferred in 4239648, out of the broad range of telomers disclosed in U.S. 4046707, the selected telomers have inherently high corrosion inhibiting properties, without the need for co-additives to boost their corrosion inhibiting effect.
Accordingly, the present invention provides a method of inhibiting corrosion of metal surfaces in contact with an aqueous system by contacting the metal surfaces with a telomer compound having the formula I:
205a2~8 O H
MO ~ 1 CH2--C ~ H
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical; and n is an average integer ranging from 1 to 60, preferably from4~o30.
Alkali metal cations M are, principally, lithium, sodium and potassium ions; alkaline earth metal atoms are, e.g., calcium, magnesium, barium or strontium; ammonium ions include, e.g. trimethylammonium, triethylammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium and bis(2-hydroxyethyl)-2-(hydroxy-3-p-nonylphenoxypropyl) ammonium ions; and quaternised amine radicals include those having the formula N~3(RaRbRCRd)4 An~3 in which Ra~ Rh, Rc and Rd are the same or different, and each is Cl-C6 alkyl, especially methyl or ethyl, or each is 2-hydroxyethyl, or one of Ra~ Rb, Rc and Rd is benzyl, and the other three of Ra~ Rb Rc and Rd are Cl-C6 alkyl, especially methyl or ethyl, and An(3 is a halide ion, especially chloride or bromide, hydroxyl or sulphate.
The compounds of formula I are known compounds, having been broadly described in US
Patent 2957~31 and, of course, in US Patent 4046707.
The compounds of formula I may be produced by reacting the appropriate molar ratio of acrylic acid, or a Cl-C6 aLkyl ester thereof, depending upon the desired value of n, with one mole of a di(CI-C4 alkyl)phosphite or diarylphosphite, in particular diethylphosphite.
The reaction may be conveniently conducted in the presence of a polymerization initiator such as bisazoisobutyronitrile; organic peroxides such as benzoyl peroxide, methylethylketone peroxide, di-tertiarybutyl peroxide and mono-butyl hydroperoxide; or oxidizing agents such as hydrogen peroxide, sodium perborate or sodium persulphate.
At completion of the reaction between diethyl phosphite and the acrylic monomer, the crude reaction mixture may be purified, if desired, by conventional techniques, for example, any excess diethyl phosphite reactant may be removed by distillation of the . " ~
: .
.,, . ~; .' -~ ' ., . . , , , ~
.. , , . ~ - -~. ..
- 4 - 2~ 3`~
reaction mixture. Moreover, any ester groupings on the acrylic moieties in the compounds of forrnula I may be converted into carboxyl functions by, e.g., acid hydrolysis. After, s~lch acid hydrolysis, the hydrolyzed prvduct may be evaporated to dryness, to provide solid material of forrnula I.
Salts Or the compounds of formula I in which some or all of the acidic hydrogens M in the compounds of formula I have been replaced by alkali metal-ammonium - or quaternised amine cations, may be prepared by mixing an aqueous or alcoholic solution containing the requisite base, in an amount which may be more than, equal to or less than the stoichiometric requirement for full replacement of the acidic hydrogens. ~e solvent for the base may then be removed, e.g. by evaporation.
Many of the aqueous systems to be treated according to the method of the presentinvention are suf~lciently basic, that the system itself is adequate to effect neutralization, so that when adding the acidic form of the compound of formula I, it is converted in situ into an alkali metal version.
The amount of the compound of formula 1, or salt thereof, used in the method according to the present invention may range e.g. from 0.1 to 50,000 ppm, preferably from 1 to 500 ppm, based on the weight of the aqueous system.
The aqueous system which is treated according to the method of the present invention may be a totally aqueous or a partly aqueous medium.
Aqueous systems which may be effectively treated according to the present invention include e.g. cooling water systems, steam generating systems, sea-water evaporators, reverse osmosis equipment, bottle washing plants, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, aqueous machining fluid formations (e.g. for use in boring, milling, reaming, broaching, drawing, turning, cutting, sewing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations), aqueous scouring systems, aqueous glycol anti-freeze systems, water/glycol hydraulic fluids; and aqueous - based polymer surface coating systems.
The compounds of formula I may be used in the method of the present invention either alone or in conjunction with other materials known to be useful in water treatment.
-s- 2~2~
In the treatment of systems which are completely aqueous, e.g. cooling water systems, steam-generating systems, sea watcr evaporator systems, hydrostatic cookers and closed circui~ heating systems, examples of further water treatment additives include one or more of fwrther corrosion inhibitors; metal deactivators; further scale inhibitors/dispersing agents; threshold agents; precipitating agents; oxygen scavengers; sequestering agents;
antifoaming agents; and biocides.
Further corrosion inhibitors which may be used include water-soluble zinc salts;phosphates; polyphosphates; phosphonic acids or their salts, e.g. hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phosphonic acid, methylamino dimethylene phosphonocarboxylic acids and their salts (e.g. those described in DE-OS
2632774), hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and those described in GB-PS 1572406; nitrates e.g. sodium nitrate; nitrites e.g. sodium nitrite;
tungstates and molybdates e.g. sodium tungstate or molybdate; silicates e.g. sodium silicate; N-acylsarcosines; N-acylimino diacetic acids; ethanolamines; fatty amines; and polycarboxylic acids, e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts), copolymers of maleic anhydride e.g. with sulphonated styrene, copolymers of acrylic acid e.g. with hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
Metal deactivators especially for copper, include benzotriazole, bis-benzotriazole or copper - deactivating derivatives of benzotriazole or tolutriazole, or their Mannich base derivatives, or mercaptobenzotriazole.
Scale inhibitors/dispersing agents include polymerized acrylic acid (or its salts), phosphino-polycarboxylic acids (e.g. those described in GB-PS 1458235), the cotelomers described in EP-PS 0150706, hydrolyzed polyacrylonitr;le, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide with acrylic and methacrylic acids, lignin sulphonic acid and its salts, tannin naphthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (e.g. those described in US-PS 4029577) styrene/maleic anhydride copolymers and sulphonated styrene homopolymers (e.g. those described in US-PS 4374733, and combinations of these).
Specific threshold agents, include 2-phosphonobutane-1,2,4-tri-carboxylic acid, HEDP, hydrolyzed polymaleic anhydride and its salts, alkyl phosphonic acids, hydroxyphosphonoacetic acid, l-aminoalkyl-l,l-diphosphonic acids and the* salts, and alkali metal polyphosphates.
.
20~238 It will be clear from the above lists that certain additive compounds, e.g.
phosphonocarboxylic acids, function both as scale inhibitors and as corrosion inhibitors.
Precipitating agent co-additives which may be used are alkali metal orthophosphates or carbonates; oxygen scavengers include alkali metal sulphites and hydrazines; sequestering agents are nitrilotriacetic acid and its salts; antifoaming agents are silicones, e.g.
polydimethylsiloxanes, distearyl sebacimide, distealyl adipamide, and related products derived from ethylene oxide and/or propylene oxide condensations, in addition to fatty alcohols such as capryl alcohol and its ethylene oxide condensates. Biocides which may be used are, e.g. amines, quaternary ammonium compounds, m-chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbonates, isothiazolines, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents, bromine and bromine release agents, and organometallic compounds such as tributyl tin oxide.
If the system to be treated according to the invention is not completely aqueous e.g. an aqueous machining fluid formulation, it may be e.g. a water dilutable cutting or grinding fluid.
The aqueous machining fluid formulations of the invention may be e.g. metal working formulations. By "metal working" we mean "reaming, broaching, drawing, spinning,cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling".
Examples of water-dilutable cutting or grinding fluids into which the corrosion inhibiting compound of formula I may be incorporated include:
a) Aqueous concentrates of one or more corrosion inhibitors, and optionally one or more anti-wear additives, used at dilutions of 1:50 to 1:100, which are usually employed as grinding fluids;
b) Polyglycols containing biocides, corrosion inhibitors and anti-wear additives which are used at dilutions of 1:20 to 1:40 for cutting operations and 1:60 to 1:80 for grinding;
c) Semi-synthetic cutting fluids similar to b) but containing in addition 10 to 25% oil with sufficient emulsifi1er to render the water diluted product translucent;
d) An emulsifiable mineral oil concentrate containing, for example, ernulsifiers, corrosion inhibitors, extreme pressure/anti-wear additives, biocides, antifoaming agents, coupling 2~a238 agents etc; they are generally diluted from 1:10 to 1:50 with water to a white opaque emulsion;
e) A product similar to d) containing less oil and more emulsifier which, on dilution to the range l :50 to 1:100, gives a translucent emulsion for cutting or grinding operations.
Mixtures of sodium nitrite and triethanolamine have been used to inhibit corrosion in metal working but, because of related toxicity problems, due e.g. to the danger of forming N-nitrosamines, and because of legal regulations in some countries relating to effluents, alternatives to the use of sodium nitrite are being sought.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation the compound of formula I may be used singly, or in admixture with other additives e.g. known further corrosion inhibitors and/or extreme pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the compound of formula I, include the following groups:
a) Organic acids, their esters or ammonium, amine, alkanolamine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, disodium sebacate, triethanolamine laurate, iso-nonanoic acid, triethanolamine salt of (p-toluene sulphonamido caproic acid), sodium N-lauroyl sarcosinate or nonyl phenoxy acetic acid;
, b) Nitrogen containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, l-hydroxyethyl-2-oleyl-imidazolines; oxazolines; triazoles, for example, benzotriazoles, triethanolamines; fatty amines; and inorganic salts, for example sodium nitrate;
c) Phosphorus containing materials such as the following types: amine phosphates, phosphonic acids or inorganic salts, for example, sodium dihydrogen phosphate or zinc phosphate;
d) Sulphur containing compounds such as the following types: sodium, calcium or barium petroleum sulphvnates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
-8- ~ ) 52~8 Examples of extreme pressure additives which may be present in the systems of the present invention include sulphur and/or phosphorus and/or halogen con~aining materials, for inslance, sulphurised sperrn oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When tliethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an arnount such that the ratio of compound of formula I to triethanolamine is from 2:1 to 1:20.
The partly-aqueous systems treated by the method of the present invention may also be aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
The aqueous surface-coating composition may be e.g. a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
Sodium nitrite and sodium benzoate have been used to inhibit flash rusting of aqueous based primer paints but, because of related toxicity problems and problems of emulsion stability at the high ionic concentrations used, industry is moving away from sodium nitrite and sodium benzoate.
In aqueous surface-coating compositions treated according to the invention the compound of formula I may be used singly, or in admixture with other additives e.g. known corrosion inhibitors, biocides, emulsifiers and/or pigments.
The further known corrosion inhibitors which may be used are e.g. those of classes a), b), c) and d) hereinbefore defined.
Examples of biocides which may be used in these aqueous systems, in addition to the compound of for nula I, include the following:
Phenols and aLlcyl- and halogenated phenols, for example pentachlorophenol, o-phenyl phenol, o-phenoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, diamines, tTiazines and ~rganometallic compounds such as organomercury compounds and organotin compounds.
Examples of pigments which may be used in these aqueous systems, in addition to the 20~238 compound of forrnula I, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as Ihe phthalocyanines.
The following Examples further illustrate the present invention. Examples A, B, C and D
relate to the preparation of compounds of forrnula I for use in the method of the present invention Example A
lOOg of ethyl acrylate and lSg of di-tert-butylperoxide are added separately, dropwise, to 138g of diethyl phosphite, over 4 hours, at 140C. This temperature is maintained for a further 2 hours, after the additions are complete. Unreacted diethyl phosphite is removed by distillation under reduced pressure, and the residue is suspended in 400g of 18% w/w hydrochloric acid, and the suspension so obtained is heated, under reflux conditions, for 48 hours.
The resulting solution is evaporated to dryness, under reduced pressure, to give 68g of product (94% of the theoretical yield based on acrylic acid).
The product obtained has an Mn = 644 and Mw = 941, giving a ratio MW/M" = 1.46.
Microanalysis of the product gives 8.15% P; corresponding to an average value of integer n =4.
Example B
Using the procedure set out in Example A, 160g of ethyl acrylate and 15g of di-tert butylperoxide are added separately, dropwise, to 55.2g of diethylphosphite to give 124g ~108% of the theoretical yield based on acrylic acid) of a product having Mn = 669 and Mw = 1019, giving a ratio MW/Mn of 1.52. Microanalysis of the product gives: 4.7% P;
colresponding to an average value of integer n = 8.
ExamPle C
Using the procedure set out in Example A, 88.9g of ethyl acrylate and 7.3g of di-tert butyl peroxide are added separately, dropwise, to 15.5g of diethyl phosphite to give 65g (103% of the theoretical yield based on acrylic acid) of a product having Mn = 732 and Mw = 2224 giving a ratio MW/MI, of 3.04. Microanalysis of the product gives: 3.15% P;
corresponding to an average value of integer n = 12.
Example D
Using the procedure described in Example A, 92.3g of ethyl acrylate and 7.2g of di-tert - l- 20~238 butyl peroxide are added separately, dropwise, to 10.6~ of diethyl phosphite to give 71g of product (107% of theoretical yield based on acrylic acid) having Ml, = 790 and Mw = 2837, giving a ratio MW/MI, = 3.59. Microanalysis of the product gives: 2.1% P; corresponding to an average value of integer n of 20.
Example E
Using the procedure set out in Example A, 43g of methyl acrylate and 7.5g of di-tert butyl peroxide are added separately, dropwise, to 55g of dimethyl phosphite to give 40g (111% of the theoretical yield based on acrylic acid) having Mn = 705 and Mw = 1102, giving a ratio MW/M,, = 1.56. Microanalysis of the product gives 7.1% P; corresponding tO an average value of integer n = S.
Examples 1 to 4 The corrosion inhibitor activities of the products of Examples A, B, C and E are evaluated in the Rotating Coupon Test using the following standard corrosive waters.
In the following, PH denotes permanent hardness, PA denotes perrnanent alkalinity, TA
denotes temporary alkalinity and TH denotes total hardness.
150 Ca 300 Ca PH 8.5 8.3 Ca2~(ppm) 150 300 Mg2+(ppm) 75 150 Cl- (ppm) 200 218 So4 2 - (ppm)200 38 In a one litre reservoir of one of the test waters, two pre-cleaned and pre-weighed mild steel coupons are rotated at a coupon velocity of 61 cms per second. The test is conducted - 11 205~2~8 over 48 hours in oxygenated water at 40C using 30 ppm of the appropriate corrosion inhibitor under test.
The coupons are removed, scrubbed without pumice, immersed for one minute in hydrochloric acid inhibited with 1% by weight of hexamine, and then rinsed, dried and reweighed. A certain loss in weight will have occurred. A blank test, i.e. immersion of mild steel coupons in the test water in the absence of any test corrosion inhibitor is carried out in each series of tests. The corrosion rates are calculated in milligrams of weight loss/square decimetre/day (m.d.d.).
The results are set out in the Table:
Table . Inhibitor Corrosion Rate (m.d.d~) Example Inhibitor in test water Concentration (ppm) 150 Ca 300 Ca None 130.2 1 Product of Ex. A 30 22.1 40.7 2 Product of Ex. B 30 31 19 3 Product of Ex. C 30 78 19 4 Product of Ex. E 30 38 35
reaction mixture. Moreover, any ester groupings on the acrylic moieties in the compounds of forrnula I may be converted into carboxyl functions by, e.g., acid hydrolysis. After, s~lch acid hydrolysis, the hydrolyzed prvduct may be evaporated to dryness, to provide solid material of forrnula I.
Salts Or the compounds of formula I in which some or all of the acidic hydrogens M in the compounds of formula I have been replaced by alkali metal-ammonium - or quaternised amine cations, may be prepared by mixing an aqueous or alcoholic solution containing the requisite base, in an amount which may be more than, equal to or less than the stoichiometric requirement for full replacement of the acidic hydrogens. ~e solvent for the base may then be removed, e.g. by evaporation.
Many of the aqueous systems to be treated according to the method of the presentinvention are suf~lciently basic, that the system itself is adequate to effect neutralization, so that when adding the acidic form of the compound of formula I, it is converted in situ into an alkali metal version.
The amount of the compound of formula 1, or salt thereof, used in the method according to the present invention may range e.g. from 0.1 to 50,000 ppm, preferably from 1 to 500 ppm, based on the weight of the aqueous system.
The aqueous system which is treated according to the method of the present invention may be a totally aqueous or a partly aqueous medium.
Aqueous systems which may be effectively treated according to the present invention include e.g. cooling water systems, steam generating systems, sea-water evaporators, reverse osmosis equipment, bottle washing plants, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, aqueous machining fluid formations (e.g. for use in boring, milling, reaming, broaching, drawing, turning, cutting, sewing, grinding, and in thread-cutting operations, or in non-cutting shaping, spinning, drawing or rolling operations), aqueous scouring systems, aqueous glycol anti-freeze systems, water/glycol hydraulic fluids; and aqueous - based polymer surface coating systems.
The compounds of formula I may be used in the method of the present invention either alone or in conjunction with other materials known to be useful in water treatment.
-s- 2~2~
In the treatment of systems which are completely aqueous, e.g. cooling water systems, steam-generating systems, sea watcr evaporator systems, hydrostatic cookers and closed circui~ heating systems, examples of further water treatment additives include one or more of fwrther corrosion inhibitors; metal deactivators; further scale inhibitors/dispersing agents; threshold agents; precipitating agents; oxygen scavengers; sequestering agents;
antifoaming agents; and biocides.
Further corrosion inhibitors which may be used include water-soluble zinc salts;phosphates; polyphosphates; phosphonic acids or their salts, e.g. hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phosphonic acid, methylamino dimethylene phosphonocarboxylic acids and their salts (e.g. those described in DE-OS
2632774), hydroxyphosphonoacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and those described in GB-PS 1572406; nitrates e.g. sodium nitrate; nitrites e.g. sodium nitrite;
tungstates and molybdates e.g. sodium tungstate or molybdate; silicates e.g. sodium silicate; N-acylsarcosines; N-acylimino diacetic acids; ethanolamines; fatty amines; and polycarboxylic acids, e.g. polymaleic acid and polyacrylic acid (and their respective alkali metal salts), copolymers of maleic anhydride e.g. with sulphonated styrene, copolymers of acrylic acid e.g. with hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers.
Metal deactivators especially for copper, include benzotriazole, bis-benzotriazole or copper - deactivating derivatives of benzotriazole or tolutriazole, or their Mannich base derivatives, or mercaptobenzotriazole.
Scale inhibitors/dispersing agents include polymerized acrylic acid (or its salts), phosphino-polycarboxylic acids (e.g. those described in GB-PS 1458235), the cotelomers described in EP-PS 0150706, hydrolyzed polyacrylonitr;le, polymerized methacrylic acid and its salts, polyacrylamide and copolymers of acrylamide with acrylic and methacrylic acids, lignin sulphonic acid and its salts, tannin naphthalene sulphonic acid/formaldehyde condensation products, starch and its derivatives, cellulose, acrylic acid / lower alkyl hydroxy-acrylate copolymers (e.g. those described in US-PS 4029577) styrene/maleic anhydride copolymers and sulphonated styrene homopolymers (e.g. those described in US-PS 4374733, and combinations of these).
Specific threshold agents, include 2-phosphonobutane-1,2,4-tri-carboxylic acid, HEDP, hydrolyzed polymaleic anhydride and its salts, alkyl phosphonic acids, hydroxyphosphonoacetic acid, l-aminoalkyl-l,l-diphosphonic acids and the* salts, and alkali metal polyphosphates.
.
20~238 It will be clear from the above lists that certain additive compounds, e.g.
phosphonocarboxylic acids, function both as scale inhibitors and as corrosion inhibitors.
Precipitating agent co-additives which may be used are alkali metal orthophosphates or carbonates; oxygen scavengers include alkali metal sulphites and hydrazines; sequestering agents are nitrilotriacetic acid and its salts; antifoaming agents are silicones, e.g.
polydimethylsiloxanes, distearyl sebacimide, distealyl adipamide, and related products derived from ethylene oxide and/or propylene oxide condensations, in addition to fatty alcohols such as capryl alcohol and its ethylene oxide condensates. Biocides which may be used are, e.g. amines, quaternary ammonium compounds, m-chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbonates, isothiazolines, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents, bromine and bromine release agents, and organometallic compounds such as tributyl tin oxide.
If the system to be treated according to the invention is not completely aqueous e.g. an aqueous machining fluid formulation, it may be e.g. a water dilutable cutting or grinding fluid.
The aqueous machining fluid formulations of the invention may be e.g. metal working formulations. By "metal working" we mean "reaming, broaching, drawing, spinning,cutting, grinding, boring, milling, turning, sawing, non-cutting shaping or rolling".
Examples of water-dilutable cutting or grinding fluids into which the corrosion inhibiting compound of formula I may be incorporated include:
a) Aqueous concentrates of one or more corrosion inhibitors, and optionally one or more anti-wear additives, used at dilutions of 1:50 to 1:100, which are usually employed as grinding fluids;
b) Polyglycols containing biocides, corrosion inhibitors and anti-wear additives which are used at dilutions of 1:20 to 1:40 for cutting operations and 1:60 to 1:80 for grinding;
c) Semi-synthetic cutting fluids similar to b) but containing in addition 10 to 25% oil with sufficient emulsifi1er to render the water diluted product translucent;
d) An emulsifiable mineral oil concentrate containing, for example, ernulsifiers, corrosion inhibitors, extreme pressure/anti-wear additives, biocides, antifoaming agents, coupling 2~a238 agents etc; they are generally diluted from 1:10 to 1:50 with water to a white opaque emulsion;
e) A product similar to d) containing less oil and more emulsifier which, on dilution to the range l :50 to 1:100, gives a translucent emulsion for cutting or grinding operations.
Mixtures of sodium nitrite and triethanolamine have been used to inhibit corrosion in metal working but, because of related toxicity problems, due e.g. to the danger of forming N-nitrosamines, and because of legal regulations in some countries relating to effluents, alternatives to the use of sodium nitrite are being sought.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation the compound of formula I may be used singly, or in admixture with other additives e.g. known further corrosion inhibitors and/or extreme pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the compound of formula I, include the following groups:
a) Organic acids, their esters or ammonium, amine, alkanolamine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, disodium sebacate, triethanolamine laurate, iso-nonanoic acid, triethanolamine salt of (p-toluene sulphonamido caproic acid), sodium N-lauroyl sarcosinate or nonyl phenoxy acetic acid;
, b) Nitrogen containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, l-hydroxyethyl-2-oleyl-imidazolines; oxazolines; triazoles, for example, benzotriazoles, triethanolamines; fatty amines; and inorganic salts, for example sodium nitrate;
c) Phosphorus containing materials such as the following types: amine phosphates, phosphonic acids or inorganic salts, for example, sodium dihydrogen phosphate or zinc phosphate;
d) Sulphur containing compounds such as the following types: sodium, calcium or barium petroleum sulphvnates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
-8- ~ ) 52~8 Examples of extreme pressure additives which may be present in the systems of the present invention include sulphur and/or phosphorus and/or halogen con~aining materials, for inslance, sulphurised sperrn oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When tliethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an arnount such that the ratio of compound of formula I to triethanolamine is from 2:1 to 1:20.
The partly-aqueous systems treated by the method of the present invention may also be aqueous surface-coating compositions e.g. primer emulsion paints and aqueous powder coatings for metallic substrates.
The aqueous surface-coating composition may be e.g. a paint such as styrene-acrylic copolymer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems.
Sodium nitrite and sodium benzoate have been used to inhibit flash rusting of aqueous based primer paints but, because of related toxicity problems and problems of emulsion stability at the high ionic concentrations used, industry is moving away from sodium nitrite and sodium benzoate.
In aqueous surface-coating compositions treated according to the invention the compound of formula I may be used singly, or in admixture with other additives e.g. known corrosion inhibitors, biocides, emulsifiers and/or pigments.
The further known corrosion inhibitors which may be used are e.g. those of classes a), b), c) and d) hereinbefore defined.
Examples of biocides which may be used in these aqueous systems, in addition to the compound of for nula I, include the following:
Phenols and aLlcyl- and halogenated phenols, for example pentachlorophenol, o-phenyl phenol, o-phenoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, diamines, tTiazines and ~rganometallic compounds such as organomercury compounds and organotin compounds.
Examples of pigments which may be used in these aqueous systems, in addition to the 20~238 compound of forrnula I, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as Ihe phthalocyanines.
The following Examples further illustrate the present invention. Examples A, B, C and D
relate to the preparation of compounds of forrnula I for use in the method of the present invention Example A
lOOg of ethyl acrylate and lSg of di-tert-butylperoxide are added separately, dropwise, to 138g of diethyl phosphite, over 4 hours, at 140C. This temperature is maintained for a further 2 hours, after the additions are complete. Unreacted diethyl phosphite is removed by distillation under reduced pressure, and the residue is suspended in 400g of 18% w/w hydrochloric acid, and the suspension so obtained is heated, under reflux conditions, for 48 hours.
The resulting solution is evaporated to dryness, under reduced pressure, to give 68g of product (94% of the theoretical yield based on acrylic acid).
The product obtained has an Mn = 644 and Mw = 941, giving a ratio MW/M" = 1.46.
Microanalysis of the product gives 8.15% P; corresponding to an average value of integer n =4.
Example B
Using the procedure set out in Example A, 160g of ethyl acrylate and 15g of di-tert butylperoxide are added separately, dropwise, to 55.2g of diethylphosphite to give 124g ~108% of the theoretical yield based on acrylic acid) of a product having Mn = 669 and Mw = 1019, giving a ratio MW/Mn of 1.52. Microanalysis of the product gives: 4.7% P;
colresponding to an average value of integer n = 8.
ExamPle C
Using the procedure set out in Example A, 88.9g of ethyl acrylate and 7.3g of di-tert butyl peroxide are added separately, dropwise, to 15.5g of diethyl phosphite to give 65g (103% of the theoretical yield based on acrylic acid) of a product having Mn = 732 and Mw = 2224 giving a ratio MW/MI, of 3.04. Microanalysis of the product gives: 3.15% P;
corresponding to an average value of integer n = 12.
Example D
Using the procedure described in Example A, 92.3g of ethyl acrylate and 7.2g of di-tert - l- 20~238 butyl peroxide are added separately, dropwise, to 10.6~ of diethyl phosphite to give 71g of product (107% of theoretical yield based on acrylic acid) having Ml, = 790 and Mw = 2837, giving a ratio MW/MI, = 3.59. Microanalysis of the product gives: 2.1% P; corresponding to an average value of integer n of 20.
Example E
Using the procedure set out in Example A, 43g of methyl acrylate and 7.5g of di-tert butyl peroxide are added separately, dropwise, to 55g of dimethyl phosphite to give 40g (111% of the theoretical yield based on acrylic acid) having Mn = 705 and Mw = 1102, giving a ratio MW/M,, = 1.56. Microanalysis of the product gives 7.1% P; corresponding tO an average value of integer n = S.
Examples 1 to 4 The corrosion inhibitor activities of the products of Examples A, B, C and E are evaluated in the Rotating Coupon Test using the following standard corrosive waters.
In the following, PH denotes permanent hardness, PA denotes perrnanent alkalinity, TA
denotes temporary alkalinity and TH denotes total hardness.
150 Ca 300 Ca PH 8.5 8.3 Ca2~(ppm) 150 300 Mg2+(ppm) 75 150 Cl- (ppm) 200 218 So4 2 - (ppm)200 38 In a one litre reservoir of one of the test waters, two pre-cleaned and pre-weighed mild steel coupons are rotated at a coupon velocity of 61 cms per second. The test is conducted - 11 205~2~8 over 48 hours in oxygenated water at 40C using 30 ppm of the appropriate corrosion inhibitor under test.
The coupons are removed, scrubbed without pumice, immersed for one minute in hydrochloric acid inhibited with 1% by weight of hexamine, and then rinsed, dried and reweighed. A certain loss in weight will have occurred. A blank test, i.e. immersion of mild steel coupons in the test water in the absence of any test corrosion inhibitor is carried out in each series of tests. The corrosion rates are calculated in milligrams of weight loss/square decimetre/day (m.d.d.).
The results are set out in the Table:
Table . Inhibitor Corrosion Rate (m.d.d~) Example Inhibitor in test water Concentration (ppm) 150 Ca 300 Ca None 130.2 1 Product of Ex. A 30 22.1 40.7 2 Product of Ex. B 30 31 19 3 Product of Ex. C 30 78 19 4 Product of Ex. E 30 38 35
Claims (9)
1. A method of inhibiting corrosion of metal surfaces in contact with an aqueoussystem, comprising contacting the metal surfaces with a telomer compound having the formula I:
I
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical: and n is an average integer ranging from 1 to 60.
I
in which M is hydrogen or an alkali or alkaline earth metal ion, an ammonium ion or a quaternised amine radical: and n is an average integer ranging from 1 to 60.
2. A method according to claim 1 in which n is an average integer ranging from 4 to 30.
3. A method according to claim 1 in which the amount of the telomer of formula I used, or salt thereof, ranges from 0.1 to 50,000 ppm, based on the weight of the aqueous system.
4. A method according to claim 3 in which the amount of the telomer of formula Iused, or salt thereof, ranges from 1 to 500 ppm, based on the weight of the aqueous system.
5. A method according to claim 1 in which the aqueous system is that comprised in a cooling water system, a steam generating system, a sea water evaporator, reverseosmosis equipment, a bottle washing plant, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous - based refrigeration systems, down-well systems, or aqueous machining fluid formulations, aqueous scouring systems, aqueous glycol antifreeze systems. water/glycol hydraulic fluids or aqueous - based polymer surface coating systems.
6. A method according to claim 1 in which the compound of formula I is used in conjunction with one or more further corrosion inhibitors; metal deactivators; scale inhibitors/ dispersing agents; threshold agents; precipitating agents; oxygen scavengers; sequestering agents; anti-foaming agents; and biocides.
7. A method according to claim 1 in which the aqueous system is an aqueous machining fluid formulation.
8. A method according to claim 7 in which the aqueous machining fluid formulation is a water-dilutable cutting or grinding fluid.
9. A method according to claim 7 in which the compound of formula I is used singly or in admixture with a further corrosion inhibitor and/or an extreme-pressure additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB909024470A GB9024470D0 (en) | 1990-11-10 | 1990-11-10 | Corrision inhibition |
| GB9024470.8 | 1990-11-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2055238A1 true CA2055238A1 (en) | 1992-05-11 |
Family
ID=10685183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002055238A Abandoned CA2055238A1 (en) | 1990-11-10 | 1991-11-08 | Corrosion inhibition |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5229030A (en) |
| EP (1) | EP0488538B1 (en) |
| JP (1) | JP3205842B2 (en) |
| AU (1) | AU645142B2 (en) |
| CA (1) | CA2055238A1 (en) |
| DE (1) | DE69119717T2 (en) |
| ES (1) | ES2090259T3 (en) |
| GB (1) | GB9024470D0 (en) |
| NO (1) | NO304747B1 (en) |
| ZA (1) | ZA918864B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629396A (en) * | 1989-01-17 | 1997-05-13 | The Dow Chemical Company | Latex containing oxazoline for industrial coatings |
| GB9021672D0 (en) * | 1990-10-05 | 1990-11-21 | Ciba Geigy Ag | Inhibition of scale |
| US5681479A (en) * | 1991-05-31 | 1997-10-28 | Fmc Corporation (Uk ) Limited | Phosphonic cotelomers and method of use |
| WO1996011291A1 (en) * | 1994-10-11 | 1996-04-18 | Fmc Corporation (Uk) Limited | Corrosion inhibiting compositions |
| US5716917A (en) * | 1996-09-24 | 1998-02-10 | Cincinnati Milacron Inc. | Machining fluid composition and method of machining |
| US6585933B1 (en) | 1999-05-03 | 2003-07-01 | Betzdearborn, Inc. | Method and composition for inhibiting corrosion in aqueous systems |
| US20060221158A1 (en) * | 2005-03-31 | 2006-10-05 | Fuji Photo Film Co., Ltd. | Aqueous recording solution for ink jet printing, ink set and ink jet printing device |
| US7727420B2 (en) * | 2005-05-17 | 2010-06-01 | Ppt Research | Corrosion inhibiting compositions |
| GB2432154B (en) * | 2005-11-10 | 2010-12-29 | Rhodia Uk Ltd | Corrosion inhibition |
| US8475757B2 (en) | 2009-04-07 | 2013-07-02 | Pro-Con International, Llc | Agents for carbon dioxide capture, agents for amine stabilization and methods of making agents for carbon dioxide capture and amine stabilization |
| US9175405B2 (en) * | 2013-03-15 | 2015-11-03 | Ecolab Usa Inc. | Corrosion control compositions and methods of mitigating corrosion |
| CN105772340B (en) | 2016-05-16 | 2019-07-05 | 京东方科技集团股份有限公司 | Liquid photocurable glue coating unit and method |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2957931A (en) * | 1949-07-28 | 1960-10-25 | Socony Mobil Oil Co Inc | Synthesis of compounds having a carbonphosphorus linkage |
| US4127483A (en) * | 1974-06-11 | 1978-11-28 | Ciba Geigy (Uk) Limited | Treatment of aqueous systems |
| GB1458235A (en) * | 1974-06-11 | 1976-12-08 | Ciba Geigy Uk Ltd | Inhibiting scale formation in aqueous systems |
| US4159946A (en) * | 1974-06-11 | 1979-07-03 | Ciba Geigy (Uk) Limited | Treatment of aqueous systems |
| DE2505435C3 (en) * | 1975-02-08 | 1980-07-31 | Hoechst Ag, 6000 Frankfurt | Use of carboxy-alkane compounds of phosphorus as corrosion inhibitors |
| US4052160A (en) * | 1975-07-23 | 1977-10-04 | Ciba-Geigy Corporation | Corrosion inhibitors |
| US4029577A (en) * | 1975-11-17 | 1977-06-14 | Betz Laboratories, Inc. | Polymers for use in water treatment |
| GB1539974A (en) * | 1976-11-10 | 1979-02-07 | Ciba Geigy Ag | Method of inhibiting corrosion and scaling of metals in contact with water |
| US4208344A (en) * | 1976-12-24 | 1980-06-17 | Ciba-Geigy Corporation | Phosphonoadipic acid additives to aqueous systems |
| DE2963154D1 (en) * | 1978-07-19 | 1982-08-12 | Ciba Geigy Ag | Corrosion inhibitors; compositions for protecting ferrous metals and the protected metals |
| DE3044214A1 (en) * | 1980-11-25 | 1982-06-24 | Bayer Ag, 5090 Leverkusen | Inhibiting scale formation and pptn. in aq. systems - by adding phosphono-poly:carboxylic acid contg. unsatd. mono: and di:carboxylic acid units |
| US4374733A (en) * | 1981-04-01 | 1983-02-22 | Betz Laboratories, Inc. | Method for treating aqueous mediums |
| US4446028A (en) * | 1982-12-20 | 1984-05-01 | Betz Laboratories, Inc. | Isopropenyl phosphonic acid copolymers used to inhibit scale formation |
| GB8400848D0 (en) * | 1984-01-13 | 1984-02-15 | Ciba Geigy Ag | Cotelomer compounds |
| US4563284A (en) * | 1984-08-06 | 1986-01-07 | The B. F. Goodrich Company | Inhibition of salt precipitation in aqueous systems |
| EP0283191A3 (en) * | 1987-03-19 | 1989-03-15 | The Dow Chemical Company | Corrosion inhibition of metals in water systems using organic phosphorous derivatives containing carboxyl groups |
| GB8822144D0 (en) * | 1988-09-21 | 1988-10-26 | Ciba Geigy Ag | Compounds |
| GB8822150D0 (en) * | 1988-09-21 | 1988-10-26 | Ciba Geigy Ag | Compounds |
| GB9021261D0 (en) * | 1990-09-29 | 1990-11-14 | Ciba Geigy Ag | Scale inhibition |
-
1990
- 1990-11-10 GB GB909024470A patent/GB9024470D0/en active Pending
-
1991
- 1991-11-05 EP EP91310222A patent/EP0488538B1/en not_active Expired - Lifetime
- 1991-11-05 DE DE69119717T patent/DE69119717T2/en not_active Expired - Fee Related
- 1991-11-05 ES ES91310222T patent/ES2090259T3/en not_active Expired - Lifetime
- 1991-11-06 US US07/788,689 patent/US5229030A/en not_active Expired - Lifetime
- 1991-11-06 AU AU87059/91A patent/AU645142B2/en not_active Ceased
- 1991-11-08 NO NO914368A patent/NO304747B1/en not_active IP Right Cessation
- 1991-11-08 ZA ZA918864A patent/ZA918864B/en unknown
- 1991-11-08 JP JP32124391A patent/JP3205842B2/en not_active Expired - Fee Related
- 1991-11-08 CA CA002055238A patent/CA2055238A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| NO914368D0 (en) | 1991-11-08 |
| AU645142B2 (en) | 1994-01-06 |
| DE69119717T2 (en) | 1997-01-23 |
| GB9024470D0 (en) | 1991-01-02 |
| EP0488538A1 (en) | 1992-06-03 |
| ES2090259T3 (en) | 1996-10-16 |
| DE69119717D1 (en) | 1996-06-27 |
| AU8705991A (en) | 1992-05-14 |
| EP0488538B1 (en) | 1996-05-22 |
| ZA918864B (en) | 1992-07-29 |
| NO914368L (en) | 1992-05-11 |
| NO304747B1 (en) | 1999-02-08 |
| JP3205842B2 (en) | 2001-09-04 |
| US5229030A (en) | 1993-07-20 |
| JPH04268086A (en) | 1992-09-24 |
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| EEER | Examination request | ||
| FZDE | Discontinued |