CA1339536C - Telomeric compound - Google Patents
Telomeric compoundInfo
- Publication number
- CA1339536C CA1339536C CA000611895A CA611895A CA1339536C CA 1339536 C CA1339536 C CA 1339536C CA 000611895 A CA000611895 A CA 000611895A CA 611895 A CA611895 A CA 611895A CA 1339536 C CA1339536 C CA 1339536C
- Authority
- CA
- Canada
- Prior art keywords
- ammonium
- compound
- formula
- c4alkyl
- hydroxy
- 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.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
Abstract
Compounds having the formula I:
(see fig.I) wherein M1, M2, M3, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal atom, ammonium or a substituted ammonium ion;
R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups; and p is an integer.
The new compounds are useful in the treatment of aqueous systems, in particular to inhibit scale deposition from aqueous systems.
(see fig.I) wherein M1, M2, M3, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal atom, ammonium or a substituted ammonium ion;
R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups; and p is an integer.
The new compounds are useful in the treatment of aqueous systems, in particular to inhibit scale deposition from aqueous systems.
Description
A-17230/=/MA 1939 Telomeric compound The present invention relates to new compounds, to their production and to their use in the treatment of aqueous systems, in particular to inhibit scale deposition from the aqueous system and/or to plevellt fouling of the aqueous system and/or to inhibit corrosion of metals in contact with the aqueous system.
In our British Patent Specification No. 1458235, there is described and claimed a method of inhibiting the precipitation of the scale forming salts of clacium, magnesium, barium and strontium from aqueous systems over a wide temperature range, comprising adding to the aqueous system a minor proportion of a product comprising a telomeric compound of the formula:
R-P-(CH2CR")n--CH2CHR"CO2H
R' CO2H
and salts thereof, wherein R" is hydrogen or a methyl or ethyl residue, R is hydrogen, a straight- or branched alkyl residue, having from 1 to 18 carbon atoms, a cycloalkyl residue having from S to 12 carbon atoms, an aryl residue, an aralkyl residue, a residue of formula:
-(CH2CR")m CH2CHR"CO2H
I
wherein R" has its previous significance and the sum n + m is an integer of at the most 100, or a residue -OX wherein X is hydrogen or a straight- or branched alkyl residue having from 1 tO 4 carbon at~ms and R' is a residue -OX wherein X has itS previous .
slgmficance.
We have now found that certain new compounds which, unexpectedly, have superior activity in the inhibition of scale deposition from aqueous systems and additionally have superior activity in the control of corrosion of metals in contact with aqueous systems.
Accordlngly, the present lnventlon provldes compounds havlng the formula I:
O -- R
Ml O ll l P CH2C CH2CH(Rl)CO2M3 C02M3 _ p whereln Ml, M2, M3, lndependently, are hydrogen, Cl-C4alkyl, phenyl, a monovalent or an equlvalent of a polyvalent metal atom, ammonlum or Cl-C4alkyl ammonlum, hydroxy Cl-C4alkyl ammonlum, bls(2-hydroxyethyl) ammonlum, trls(2-hydroxyethyl) ammonlum, bls(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonlum or 2-hydroxy-3-p-nonylphenoxy propyl ammonlum;
Rl ls Cl-C4alkyl substltuted by one or more hydroxy or carboxyl groups and p ls an lnteger.
E.g. one or more of preferably all three of Ml, M2 and M3 are hydrogen, a monovalent or an equlvalent of a polyvalent metal atom, ammonlum or a substltuted ammonlum lon.
p ls an lnteger ranglng e.g. from 1 to 1000, preferably ranglng from 1 to 99 and most preferred ranglng from 1 to 20.
When one or more of Ml, M2 and M3 ls a metal atom, they may be e.g. an alkall metal atom or an alkallne earth metal. Typlcal alkall metal atoms are e.g. sodlum and potasslum atoms and typlcal alkallne earth metal atoms are e.g. calclum, barlum and strontlum atoms. Substltuted ammonlum lons lnclude e.g. trlmethylammonlum, trlethylammonlum, bls(2-hydroxyethyl) ammonlum, trls(2-hydroxyethyl) ammonlum and bls(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonlum lons.
iD
1339~36 When one or more of M1, Mz and M3 is a C1-C~alkyl residue, they may be e.g. methyl, ethylr n-propyl,1-propyl, n-butyl, i-butyl or tert-butyl.
When R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups, it may be e.g. hydroxymethyl, 2-hydroxypropyl, carboxymethyl, carboethoxylmethyl !
2-carboxyethyl, 2-carboethoxyethyl, 1,2-dicarboxyethyl, 1,2-dlcarbomethoxyethyl, 2,4-dicarboxybutyl or 2,4-di-carbomethoxybutyl. Preferred for Rl are carboxymethyl, carboxyethyl and 1,2-dlcarboxyethyl.
The new compounds of formula I may be produced by reactlng p+1 moles of a compound of formula II:
CH2=C(Rl)-co2R3 II
and one mole of a compound havin~ the formula III:
o Il /~R4 H-P III
wherein R1 has its previous significance, and R3, R4 and R5, independently, are hydrogen, C1-C4alkyl, phenyl a monovalent or an equivalent of a polyvalent metal lon, ammonium or a substltuted ammonium ion as defined above, or R4 and R5 may be linked by a -CH2CH2-residue to form a cyclic rlng structure.
Typical metal ions R3, R4 and R5, and optionally substltuted ammonlum ions R3, R4 and R5, respectively, are those previously indicated under the definition of M1, M2 and M3.
'~,C
The reaction may be effected, ln the presence or absence of a solvent, and in the presence of a free radical initlator e.g. organic peroxldes such as dl-tert.butyl peroxlde, benzoyl peroxlde, blsazolsobutyronitrile, hydrogen peroxide, sodium peroxide and sodium perborate. If a solvent is used, thls may be e.g. water, an aromatlc hydrocarbon such as toluene; dioxan; a ketone such as 2-butanone; or an alcohol e.g. isopropanol; each optlonally ln admlxture wlth water.
The products of the process accordlng to the present lnventlon are water-soluble. When, a reactant of formula II
or III ls used whlch contalns a group R3, R4 or R5 whlch ls Cl-C4alkyl or phenyl, such groups may be partlally or fully hydrolysed to subsequently produce a compound of formula I
contalnlng the correspondlng groups M1, M2 and M3, whereln M1, M2 and M3 have thelr prevlous slgnlflcance. Such compounds of formula I are produced by the sald hydrolysls followed by substltutlon of some or all of the acldlc hydrogen atoms so obtalned, by catlons of the salt-formlng bases, herelnbefore deflned.
Reactants of formula II lnclude ltaconlc acld, dl-methyl ltaconate, but-1-en-2,4-dlcarboxylic acid, diethyl but-1-ene-2,4-dlcarboxylate, hex-1-en-2,4,6-tricarboxylic acid, trlethyl-hex-l-en-2,4,6-tricarboxylate, but-1-en-2,3,4-trlcarboxyllc acid, trlmethyl but-l-en-1,3,4-trlcarboxylate, 2-hydroxymethyl acryllc acld and 2-hydroxyethyl acryllc ,,C
I339~36 acid.
Reactants of formula III include phosphorous acid, di-ethyl phosphite, di-methylphosphite, di-butyl phosphite, di-phenyl phosphite, ethylene phosphite and sodium hydrogen phosphite.
The compounds of formula I are effective in inhibiting deposition of scale and precipitation of salts from aqueous solutions. The compounds are particularly effective in combatting scale-forming salts derived from calcium, magnesium, barium, or strontium cations and anions such as sulphate, carbonate, hydroxide, phosphate or silicate. The compounds of formula I are especially effective in inhibiting deposition of calcium sulphate, magnesium hydroxide, calcium phosphate and calcium carbonate scale.
The compounds of formula I also function as dispersing agents and/or antifoulants towards common deposits found in water used in commercial plants e.g. industrial boilers, cooling water systems, gas scrubbing plants and aqueous slurries found in china clay operations.
Examples of such deposits are iron oxides, calcium and magnesium deposits e.g. their carbonates, sulphates, oxalates and phosphates, and silt, alumina, silicates and clays.
The compounds of formula I also provide excellent inhibition against corrosion of metals, especially ferrous metals, in contact with water.
Still further, the compounds of formula I are useful for inhibiting the thick velvety coating (sealing smut) which can be deposited over the surface of aluminium during the sealing of anodically produced oxide layers on the aluminium, using hot or boiling water.
The products of the process of the present invention are obtained as solutions. For the purpose of isolation they may be subjected to partial or complete evaporation under reduced pressure. The reaction products mav be used as the telomeric products in the method of the irlvention as descl ibed hereinafter.
Salt forms of the compounds of formula I in which some or all of the acidic hydrogens in the compounds of formula I have been replaced by the cations derived from the salt forming bases hereinbefore defined, may be prepared by mixing an aqueous or alcoholic solution of the compound of formula I with an aqueous or alcoholic solution of the compound of formula I with an aqueous or alcoholic solution containing an amount of the 133~536 requisite base in excess of, equal to or less than the stoichiometric requirement. The solvent may then be removed by evaporation. In many of the water-containing systems where inhibitors of this invention would prove useful, the water is sufficiently alkaline to effect neutralisation and only the product of the invention need be added.
The present invention also provides a method of treating an aqueous system comprising adding to the system a telomer compound of formula I.
In practice, the amount of the compound of formula I used to treat the aqueous system may vary according to the protective function which the compound is required to perform.
For example, for corrosion-inhibiting protective treatments, optionally with simultaneous scale-inhibiting treatments, the amount of the compound of formula I added to the aqueous system may range from 0.1 to 50'000 ppm (0.00001 to 5 % by weight), preferably from 1 to S00 ppm (0.0001 to O.OS % by weight), based on the weight of the aqueous system.
For solely anti-scale treatments, the amount of the compound of formula I added is conveniently from 1 to 200, preferably 1 to 30 ppm, based on the aqueous system. For most relatively dilute aqueous dispersions to be treated, the amount of compound of formula I to be added as dispersant/antifoulant is conveniently from 1 to 200 ppm, preferably 2 to 20 ppm by weight. Aqueous slurries to be treated, however, may require much higher levels of compound of formula I e.g. from 0.1 to 5 % by weight on total solids - which can be as high as 70 % by weight of the total aqueous system.
When used to inhibit the deposition of scale and the precipitation of salts from aqueous solutions, the compounds of formula I, or salts thereof, are particularly effective in inhibiting deposition of scale-forming salts derived from calcium, magnesium, barium or strontium cations, and anions such as sulphate, carbonate, hydroxide, phosphate and silicate.
With respect to aqueous system which may be treated according to the present invenion, of particular interest with respect to combined corrosion inhibition and anti-scale treatments are cooling water system, steam generating systems, sea-water evaporators, reverse osmosis equipment, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous-based refrigeration systems and down-well systems; for corrosion 1339~36 inhibition treatments alone, aqueous systems of particular interest include aqueous m~Ghining fluid formulations (e.g. for use in boring, milling, reaming, broaching, drawings, spinning, turning, cutting, sawing, grinding, and thread-cutting operations or in non-cutting shaping in drawing or rolling operations) aqueous scouring systems, engine coolants including aqueous glycol antifreeze systems, water/glycol hydraulic fluids; and aqueous based polymer surface-coating systems/or solvent-based polymer systems, e.g.
those containing tetrahydl~rul~n, ketones or aL~oxyaL~anols.
The inhibitor compound of formula I used according to the invention may be used alone, or in conjunction with other compounds known to be useful in the treatment of aqueous systems.
In the treatment of systems which are completely aqueous, such as cooling water systems, air-conditioning systems, steam-generating systems, sea-water evaporator systems, hydrostatic cookers, and closed circuit heating or refrigerant systems, further corrosion inhibitors may be used such as, for example, water soluble zinc salts; phosphates;
polyphosphates; phosphonic acids and their salts, for example, hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phopshonic acid and methylamino dimethylene phosphonocarboxylic acids and their salts, for example, those described in German Offenlegungsschrift 2632774, hydroxyphosphonoacetic acid, 2-phosphonobutane- 1,2,4-tri-carboxlyic acid and those disclosed in GB 1572406; nitrates, for example, sodium nitrate; nitrites, e.g. sodium nitrite; molybdates, e.g. sodium molybdate, tungstates;
silicates, e.g. sodium silicate; benzotriazole, bis-benzotriazole or copper deactivating benzotriazole or tolutriazole derivatives or their Mannich base derivatives;
mercaptobenzotriazole; N-acyl sarcosines; N-acylimino diacetic acids; ehtanolamines;
fatty amines; and polycarboxylic acids, for example, polymaleic acid and polyacrylic acid, as well as their respective alkali metal salts, copolymers of maleic anhydride, e.g.
copolymers o maleic anhydride and sulfonated styrene, copolymers of acrylic acid, e.g.
copolymers of acrylic acid an hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers. Moreover"n such completely aqueous systems, the inhibitor used according to the invention may be used in conjunction with further dispersing and/or threshold agents, e.g. polymerised acrylic acid (or its salts), phosphino-polycarboxylic acids (as described and claimed in British Patent 1458235), the cotelomeric compounds described in European Patent Application No. 0150706, hydrolysed polyacrylonitrile, polymerised meth-acrylic acid and its salts, polyacrylamide and copolymers thereof from acrylic and methacrylic acids, lignin sulphonic acid and its 1339~i36 salts, tannin, naphthalene sulphonie aeid/formaldehyde eondensation produets, stareh and its derivatives, eellulose, aerylie aeid/lower alkyl hydroxy-acrylate eopolymers, e.g. those deseribed in US Patent Speeifieation No. 4029577, styrene/maleie anhydride eopolymers and sulfonated styrene homopolymers, e.g. those deseribed in US Patent Speeifieation No. 4374733 and eombinations thereof. Speeifie threshold agents, sueh as for example, 2-phosphono-butane-1,2,4-tri-earboxylie aeid (PBSAM), hydroxyethyl diphosphonie aeid (HEDP), hydrolysed polymaleie anhydride and its salts, alkyl phosphonie aeids, hydroxy-phosphonoaeetie aeid, 1-aminoalkyl-1,1-diphosphonie aeids and their salts, and alkali metal polyphosphates, may also be used.
Partieularly interesting additive paekages are those eomprising eompounds of formula I
with one or more of polymaleie aeid or polyaerylie aeid or their eopolymers, or substituted eopolymers, hydroxyphosphonoaeetie acid, HEDP, PBSAM, triazoles sueh as tolutriazole, molybdates and nitrites.
Precipitating agents such as alkali metal orthophosphates, carbonates; oxygen scavengers such as alkali metal sulphites and hydrazines; sequestering agents such as nitrilotriacetic acid and its salts; antifoaming agents such as silicones, e.g. polydimethylsiloxanes, distearylseb~cami~le, distearyl adipamide and related products derived from ethylene oxide and/or propylene oxide condensation, in addition to fatty alcohols, such as capryl alcohols and their ethylene oxide condenstes; and biocides, e.g. amines, quaternary ammonium compounds, chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbamates, isothiazolones, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents and organometallic compounds such as tributyl tin oxide, may be used.
If the system to be treated by the method of 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 maching 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 eorrosion inhibiting eombination may be incorporated include:
a) aqueous eoneentrates of one or more eorrosion inhibitors, and optionally one or more 133953~
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 emulsifier to render the water diluted product translucent;
d) an emulsifiable mineral oil concentrate containing, for example, em~ ifiers, corrosion inhibitors, extreme pressure/anti-wear additives, biocides, anti-foaming agents, coupling agents etc; they are generally diluted from 1:10 to 1:50 with water to a white opaque emulslon;
e) a product similar to (d) containing less oil and more emulsifier which on dilution to the range 1:50 to 1:100 gives a translucent emulsion for cutting or grinding operations.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation the inhibitor of formula I used according to the invention may be used singly, or in ad~ ul~ with other additives, e.g. known further corrosioninhibitors and/or extreme-pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the inhibitor composition used according to the invention, include the following groups:
a) Organic acids, their esters or ammonium, amine, alkanol-amine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, disodium sebacate, triethanolamine laurate, isononanoic acid, triethanolamine salt of (p-toluene sulphonamido caproic acid), triethanolamine salt of benzene sulphonamido caproic acid, triethanolamine salts of 5-ketocarboxylic acid derivatives as described in European Patent No. 41927, sodium N
lauroyl sarcosinate or nonyl phenoxy acetic acid;
b) Nitrogen-containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, 1-hydroxy-ethyl-2-oleyl-imidazolines, oxazolines; triazoles for exam~le, benzotriazoles; or their Mannich base derivatives, triethanolamines; fatty amines; inorganic salts, for example, sodium nitrate; and the carboxy-triazine compounds described in European Patent Application No. 46139;
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 1339~36 petroleum sulphonates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
Examples of extreme pressure additives which may be present in the systems treated according to the present invention include sulphur and/or phosphorus and/or halogen containing materials, for instance, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When triethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an amount such that the ratio of inhibitor composition 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. emulsion paints and aqueous powder coatings for metallic substrates.
The aqeous surface-coating composition may be, e.g. a paint such as a styrene-acrylic copolmyer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems, to coat a metal substrate. The inhibitor composition used according to the invention may be employed to prevent flash rusting of the metal substrate duringapplication of the surface coating and to prevent subsequent corrosion during use of the coated metal.
In aqueous surface-coating compositions treated by the method of the invention the inhibitor composition 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 formula I, include the following:
Phenols, and alkyl- and halogenated phenols, for example, pentachlorophenol, o-phenylphenol, o-phenoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, 1~39536 diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.
Examples of emlllsifiçrs for aqueous surface coatings include alkyl sulfates, alkyl sulfonates, ether-alcohol sulphonates, di-n-alkyl sulphosumates and polyoxyethylen nonylphenyl ethers.
Examples of pigments which may be used in these aqueous systems, in addition to the compound of formula I, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
As already indicated compounds of formula I also function as dispersing agents and/or antifoulants towards common deposits, e.g. iron oxides and/or iron salts, calcium and magnesium deposits, e.g. their carbonates, sulphates, oxalates and phosphates, and silt, alumina, silicates and clays found in such waters.
In particular, the method of the present invention may be applied to disperse deposits in an aqueous system containing S to 1500 ppm by weight of calcium ion as well as suspended solids. This aspect of the present invention finds particular use in the china clay industry in which it is important to obtain slurries which will not appreciably separate out during transportation from the clay pits to the user. At high concentrations of suspended solids in these slurries, the compounds of formula I have been found to disperse china clay and to be of value as "in-process" dispersants and as grinding aids.
The following Examples further illustrate the present invention. All parts and percentages are by weight, unless stated otherwise.
Example 1: To 12.1 parts by weight of di-ethylphosphite are added, separately, 70 parts by weight of diethyl but-1-en-2,4-dicarboxylate and 5.75 parts by weight of di-tert-butyl-peroxide, dropwise, over 3 hours, with stirring at 140~C. The temperature is maintained at 140~C for a further 2 hours after the additions are complete. Unreacted di-ethyl-phosphite is removed by distillation under reduced pressure up to 200~/130 Pa and the residual liquid is suspended in 400 parts by weight of concentrated hydrochloric acid, and the mixture heated under reflux conditions for 18 hours.
The resulting solution is evaporated to dryness under reduced pressure at 100~C/1600 Pa 133~36 to give 53 parts by weight of a solid polymer having a molecular weight of 1430.
The absence of phosphorous acid and the presence of the phosphonic acid telogen is proven be 31p nmr analysis (multiple signals at 28 ppm).
Example 2: Following the procedure described in Example 1, from 23 parts by weight of diethylphosphite, 52.7 parts by weight of di-methyl itaconate ad 5.3 parts by weight of di-tert-butyl-peroxide there are obtained 44.5 parts by weight of a polymer having a molecular weight of 590 and a 31p multiple spectrum around 25-30 ppm.
Example 3: Calcium carbonate (cooling water) threshold test Test Conditions Test temperature 70~C
Test duration 30 minutes Aeration rate 500 cc/min (per 100 ml) Calcium 150 ppm as Ca2+
Magnesium 45 ppm as Mg2+
Carbonate 51 ppm as co32-Bicarbonate 269 ppm as -HCO3 Test additive 1 ppm The test is designed to assess the ability of an additive to inhibit the precipitation of CaCO3. The water composition simulates cooling water and the high temprature represents the conditions which exist close to a heat exchanger. Air bubbling is used to increase the severity of the test conditions.
A volume of solution containing sodium carbonate and sodium bicarbonate is mixed with an equal volume of a solution containing calcium chloride and magnesium chloride which already contains the test additive. The resulting test solution, through which air is bubbled at a contant rate, is stored at 70~C for 30 minutes. After this tirrle, the solution is filtered and the calcium remaining in the filtrate is determined by EDTA titration.
Each test is carried out in duplicate, and the first test is a standard test which determines the actual Ca2+ concentration in the test.
13~36 titre of test-titre of blank % CaC03 inhibition = x 100 titre of standard-titre of blank The standard and blank titres are usually 15-16 ml and 5-6 ml, respectively.
The product of Example 1, at 1 ppm level of addition, gave a % CaC03 inhibition of 63.
In our British Patent Specification No. 1458235, there is described and claimed a method of inhibiting the precipitation of the scale forming salts of clacium, magnesium, barium and strontium from aqueous systems over a wide temperature range, comprising adding to the aqueous system a minor proportion of a product comprising a telomeric compound of the formula:
R-P-(CH2CR")n--CH2CHR"CO2H
R' CO2H
and salts thereof, wherein R" is hydrogen or a methyl or ethyl residue, R is hydrogen, a straight- or branched alkyl residue, having from 1 to 18 carbon atoms, a cycloalkyl residue having from S to 12 carbon atoms, an aryl residue, an aralkyl residue, a residue of formula:
-(CH2CR")m CH2CHR"CO2H
I
wherein R" has its previous significance and the sum n + m is an integer of at the most 100, or a residue -OX wherein X is hydrogen or a straight- or branched alkyl residue having from 1 tO 4 carbon at~ms and R' is a residue -OX wherein X has itS previous .
slgmficance.
We have now found that certain new compounds which, unexpectedly, have superior activity in the inhibition of scale deposition from aqueous systems and additionally have superior activity in the control of corrosion of metals in contact with aqueous systems.
Accordlngly, the present lnventlon provldes compounds havlng the formula I:
O -- R
Ml O ll l P CH2C CH2CH(Rl)CO2M3 C02M3 _ p whereln Ml, M2, M3, lndependently, are hydrogen, Cl-C4alkyl, phenyl, a monovalent or an equlvalent of a polyvalent metal atom, ammonlum or Cl-C4alkyl ammonlum, hydroxy Cl-C4alkyl ammonlum, bls(2-hydroxyethyl) ammonlum, trls(2-hydroxyethyl) ammonlum, bls(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonlum or 2-hydroxy-3-p-nonylphenoxy propyl ammonlum;
Rl ls Cl-C4alkyl substltuted by one or more hydroxy or carboxyl groups and p ls an lnteger.
E.g. one or more of preferably all three of Ml, M2 and M3 are hydrogen, a monovalent or an equlvalent of a polyvalent metal atom, ammonlum or a substltuted ammonlum lon.
p ls an lnteger ranglng e.g. from 1 to 1000, preferably ranglng from 1 to 99 and most preferred ranglng from 1 to 20.
When one or more of Ml, M2 and M3 ls a metal atom, they may be e.g. an alkall metal atom or an alkallne earth metal. Typlcal alkall metal atoms are e.g. sodlum and potasslum atoms and typlcal alkallne earth metal atoms are e.g. calclum, barlum and strontlum atoms. Substltuted ammonlum lons lnclude e.g. trlmethylammonlum, trlethylammonlum, bls(2-hydroxyethyl) ammonlum, trls(2-hydroxyethyl) ammonlum and bls(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonlum lons.
iD
1339~36 When one or more of M1, Mz and M3 is a C1-C~alkyl residue, they may be e.g. methyl, ethylr n-propyl,1-propyl, n-butyl, i-butyl or tert-butyl.
When R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups, it may be e.g. hydroxymethyl, 2-hydroxypropyl, carboxymethyl, carboethoxylmethyl !
2-carboxyethyl, 2-carboethoxyethyl, 1,2-dicarboxyethyl, 1,2-dlcarbomethoxyethyl, 2,4-dicarboxybutyl or 2,4-di-carbomethoxybutyl. Preferred for Rl are carboxymethyl, carboxyethyl and 1,2-dlcarboxyethyl.
The new compounds of formula I may be produced by reactlng p+1 moles of a compound of formula II:
CH2=C(Rl)-co2R3 II
and one mole of a compound havin~ the formula III:
o Il /~R4 H-P III
wherein R1 has its previous significance, and R3, R4 and R5, independently, are hydrogen, C1-C4alkyl, phenyl a monovalent or an equivalent of a polyvalent metal lon, ammonium or a substltuted ammonium ion as defined above, or R4 and R5 may be linked by a -CH2CH2-residue to form a cyclic rlng structure.
Typical metal ions R3, R4 and R5, and optionally substltuted ammonlum ions R3, R4 and R5, respectively, are those previously indicated under the definition of M1, M2 and M3.
'~,C
The reaction may be effected, ln the presence or absence of a solvent, and in the presence of a free radical initlator e.g. organic peroxldes such as dl-tert.butyl peroxlde, benzoyl peroxlde, blsazolsobutyronitrile, hydrogen peroxide, sodium peroxide and sodium perborate. If a solvent is used, thls may be e.g. water, an aromatlc hydrocarbon such as toluene; dioxan; a ketone such as 2-butanone; or an alcohol e.g. isopropanol; each optlonally ln admlxture wlth water.
The products of the process accordlng to the present lnventlon are water-soluble. When, a reactant of formula II
or III ls used whlch contalns a group R3, R4 or R5 whlch ls Cl-C4alkyl or phenyl, such groups may be partlally or fully hydrolysed to subsequently produce a compound of formula I
contalnlng the correspondlng groups M1, M2 and M3, whereln M1, M2 and M3 have thelr prevlous slgnlflcance. Such compounds of formula I are produced by the sald hydrolysls followed by substltutlon of some or all of the acldlc hydrogen atoms so obtalned, by catlons of the salt-formlng bases, herelnbefore deflned.
Reactants of formula II lnclude ltaconlc acld, dl-methyl ltaconate, but-1-en-2,4-dlcarboxylic acid, diethyl but-1-ene-2,4-dlcarboxylate, hex-1-en-2,4,6-tricarboxylic acid, trlethyl-hex-l-en-2,4,6-tricarboxylate, but-1-en-2,3,4-trlcarboxyllc acid, trlmethyl but-l-en-1,3,4-trlcarboxylate, 2-hydroxymethyl acryllc acld and 2-hydroxyethyl acryllc ,,C
I339~36 acid.
Reactants of formula III include phosphorous acid, di-ethyl phosphite, di-methylphosphite, di-butyl phosphite, di-phenyl phosphite, ethylene phosphite and sodium hydrogen phosphite.
The compounds of formula I are effective in inhibiting deposition of scale and precipitation of salts from aqueous solutions. The compounds are particularly effective in combatting scale-forming salts derived from calcium, magnesium, barium, or strontium cations and anions such as sulphate, carbonate, hydroxide, phosphate or silicate. The compounds of formula I are especially effective in inhibiting deposition of calcium sulphate, magnesium hydroxide, calcium phosphate and calcium carbonate scale.
The compounds of formula I also function as dispersing agents and/or antifoulants towards common deposits found in water used in commercial plants e.g. industrial boilers, cooling water systems, gas scrubbing plants and aqueous slurries found in china clay operations.
Examples of such deposits are iron oxides, calcium and magnesium deposits e.g. their carbonates, sulphates, oxalates and phosphates, and silt, alumina, silicates and clays.
The compounds of formula I also provide excellent inhibition against corrosion of metals, especially ferrous metals, in contact with water.
Still further, the compounds of formula I are useful for inhibiting the thick velvety coating (sealing smut) which can be deposited over the surface of aluminium during the sealing of anodically produced oxide layers on the aluminium, using hot or boiling water.
The products of the process of the present invention are obtained as solutions. For the purpose of isolation they may be subjected to partial or complete evaporation under reduced pressure. The reaction products mav be used as the telomeric products in the method of the irlvention as descl ibed hereinafter.
Salt forms of the compounds of formula I in which some or all of the acidic hydrogens in the compounds of formula I have been replaced by the cations derived from the salt forming bases hereinbefore defined, may be prepared by mixing an aqueous or alcoholic solution of the compound of formula I with an aqueous or alcoholic solution of the compound of formula I with an aqueous or alcoholic solution containing an amount of the 133~536 requisite base in excess of, equal to or less than the stoichiometric requirement. The solvent may then be removed by evaporation. In many of the water-containing systems where inhibitors of this invention would prove useful, the water is sufficiently alkaline to effect neutralisation and only the product of the invention need be added.
The present invention also provides a method of treating an aqueous system comprising adding to the system a telomer compound of formula I.
In practice, the amount of the compound of formula I used to treat the aqueous system may vary according to the protective function which the compound is required to perform.
For example, for corrosion-inhibiting protective treatments, optionally with simultaneous scale-inhibiting treatments, the amount of the compound of formula I added to the aqueous system may range from 0.1 to 50'000 ppm (0.00001 to 5 % by weight), preferably from 1 to S00 ppm (0.0001 to O.OS % by weight), based on the weight of the aqueous system.
For solely anti-scale treatments, the amount of the compound of formula I added is conveniently from 1 to 200, preferably 1 to 30 ppm, based on the aqueous system. For most relatively dilute aqueous dispersions to be treated, the amount of compound of formula I to be added as dispersant/antifoulant is conveniently from 1 to 200 ppm, preferably 2 to 20 ppm by weight. Aqueous slurries to be treated, however, may require much higher levels of compound of formula I e.g. from 0.1 to 5 % by weight on total solids - which can be as high as 70 % by weight of the total aqueous system.
When used to inhibit the deposition of scale and the precipitation of salts from aqueous solutions, the compounds of formula I, or salts thereof, are particularly effective in inhibiting deposition of scale-forming salts derived from calcium, magnesium, barium or strontium cations, and anions such as sulphate, carbonate, hydroxide, phosphate and silicate.
With respect to aqueous system which may be treated according to the present invenion, of particular interest with respect to combined corrosion inhibition and anti-scale treatments are cooling water system, steam generating systems, sea-water evaporators, reverse osmosis equipment, paper manufacturing equipment, sugar evaporator equipment, soil irrigation systems, hydrostatic cookers, gas scrubbing systems, closed circuit heating systems, aqueous-based refrigeration systems and down-well systems; for corrosion 1339~36 inhibition treatments alone, aqueous systems of particular interest include aqueous m~Ghining fluid formulations (e.g. for use in boring, milling, reaming, broaching, drawings, spinning, turning, cutting, sawing, grinding, and thread-cutting operations or in non-cutting shaping in drawing or rolling operations) aqueous scouring systems, engine coolants including aqueous glycol antifreeze systems, water/glycol hydraulic fluids; and aqueous based polymer surface-coating systems/or solvent-based polymer systems, e.g.
those containing tetrahydl~rul~n, ketones or aL~oxyaL~anols.
The inhibitor compound of formula I used according to the invention may be used alone, or in conjunction with other compounds known to be useful in the treatment of aqueous systems.
In the treatment of systems which are completely aqueous, such as cooling water systems, air-conditioning systems, steam-generating systems, sea-water evaporator systems, hydrostatic cookers, and closed circuit heating or refrigerant systems, further corrosion inhibitors may be used such as, for example, water soluble zinc salts; phosphates;
polyphosphates; phosphonic acids and their salts, for example, hydroxyethyl diphosphonic acid (HEDP), nitrilotris methylene phopshonic acid and methylamino dimethylene phosphonocarboxylic acids and their salts, for example, those described in German Offenlegungsschrift 2632774, hydroxyphosphonoacetic acid, 2-phosphonobutane- 1,2,4-tri-carboxlyic acid and those disclosed in GB 1572406; nitrates, for example, sodium nitrate; nitrites, e.g. sodium nitrite; molybdates, e.g. sodium molybdate, tungstates;
silicates, e.g. sodium silicate; benzotriazole, bis-benzotriazole or copper deactivating benzotriazole or tolutriazole derivatives or their Mannich base derivatives;
mercaptobenzotriazole; N-acyl sarcosines; N-acylimino diacetic acids; ehtanolamines;
fatty amines; and polycarboxylic acids, for example, polymaleic acid and polyacrylic acid, as well as their respective alkali metal salts, copolymers of maleic anhydride, e.g.
copolymers o maleic anhydride and sulfonated styrene, copolymers of acrylic acid, e.g.
copolymers of acrylic acid an hydroxyalkylated acrylic acid, and substituted derivatives of polymaleic and polyacrylic acids and their copolymers. Moreover"n such completely aqueous systems, the inhibitor used according to the invention may be used in conjunction with further dispersing and/or threshold agents, e.g. polymerised acrylic acid (or its salts), phosphino-polycarboxylic acids (as described and claimed in British Patent 1458235), the cotelomeric compounds described in European Patent Application No. 0150706, hydrolysed polyacrylonitrile, polymerised meth-acrylic acid and its salts, polyacrylamide and copolymers thereof from acrylic and methacrylic acids, lignin sulphonic acid and its 1339~i36 salts, tannin, naphthalene sulphonie aeid/formaldehyde eondensation produets, stareh and its derivatives, eellulose, aerylie aeid/lower alkyl hydroxy-acrylate eopolymers, e.g. those deseribed in US Patent Speeifieation No. 4029577, styrene/maleie anhydride eopolymers and sulfonated styrene homopolymers, e.g. those deseribed in US Patent Speeifieation No. 4374733 and eombinations thereof. Speeifie threshold agents, sueh as for example, 2-phosphono-butane-1,2,4-tri-earboxylie aeid (PBSAM), hydroxyethyl diphosphonie aeid (HEDP), hydrolysed polymaleie anhydride and its salts, alkyl phosphonie aeids, hydroxy-phosphonoaeetie aeid, 1-aminoalkyl-1,1-diphosphonie aeids and their salts, and alkali metal polyphosphates, may also be used.
Partieularly interesting additive paekages are those eomprising eompounds of formula I
with one or more of polymaleie aeid or polyaerylie aeid or their eopolymers, or substituted eopolymers, hydroxyphosphonoaeetie acid, HEDP, PBSAM, triazoles sueh as tolutriazole, molybdates and nitrites.
Precipitating agents such as alkali metal orthophosphates, carbonates; oxygen scavengers such as alkali metal sulphites and hydrazines; sequestering agents such as nitrilotriacetic acid and its salts; antifoaming agents such as silicones, e.g. polydimethylsiloxanes, distearylseb~cami~le, distearyl adipamide and related products derived from ethylene oxide and/or propylene oxide condensation, in addition to fatty alcohols, such as capryl alcohols and their ethylene oxide condenstes; and biocides, e.g. amines, quaternary ammonium compounds, chlorophenols, sulphur-containing compounds such as sulphones, methylene bis thiocyanates and carbamates, isothiazolones, brominated propionamides, triazines, phosphonium compounds, chlorine and chlorine-release agents and organometallic compounds such as tributyl tin oxide, may be used.
If the system to be treated by the method of 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 maching 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 eorrosion inhibiting eombination may be incorporated include:
a) aqueous eoneentrates of one or more eorrosion inhibitors, and optionally one or more 133953~
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 emulsifier to render the water diluted product translucent;
d) an emulsifiable mineral oil concentrate containing, for example, em~ ifiers, corrosion inhibitors, extreme pressure/anti-wear additives, biocides, anti-foaming agents, coupling agents etc; they are generally diluted from 1:10 to 1:50 with water to a white opaque emulslon;
e) a product similar to (d) containing less oil and more emulsifier which on dilution to the range 1:50 to 1:100 gives a translucent emulsion for cutting or grinding operations.
For those partly-aqueous systems in which the aqueous system component is an aqueous machining fluid formulation the inhibitor of formula I used according to the invention may be used singly, or in ad~ ul~ with other additives, e.g. known further corrosioninhibitors and/or extreme-pressure additives.
Examples of other corrosion inhibitors which may be used in these aqueous systems, in addition to the inhibitor composition used according to the invention, include the following groups:
a) Organic acids, their esters or ammonium, amine, alkanol-amine and metal salts, for example, benzoic acid, p-tert-butyl benzoic acid, disodium sebacate, triethanolamine laurate, isononanoic acid, triethanolamine salt of (p-toluene sulphonamido caproic acid), triethanolamine salt of benzene sulphonamido caproic acid, triethanolamine salts of 5-ketocarboxylic acid derivatives as described in European Patent No. 41927, sodium N
lauroyl sarcosinate or nonyl phenoxy acetic acid;
b) Nitrogen-containing materials such as the following types: fatty acid alkanolamides;
imidazolines, for example, 1-hydroxy-ethyl-2-oleyl-imidazolines, oxazolines; triazoles for exam~le, benzotriazoles; or their Mannich base derivatives, triethanolamines; fatty amines; inorganic salts, for example, sodium nitrate; and the carboxy-triazine compounds described in European Patent Application No. 46139;
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 1339~36 petroleum sulphonates, or heterocyclics, for example, sodium mercaptobenzothiazole.
Nitrogen containing materials, particularly triethanolamine, are preferred.
Examples of extreme pressure additives which may be present in the systems treated according to the present invention include sulphur and/or phosphorus and/or halogen containing materials, for instance, sulphurised sperm oil, sulphurised fats, tritolyl phosphate, chlorinated paraffins or ethoxylated phosphate esters.
When triethanolamine is present in the aqueous systems treated according to the present invention, it is preferably present in an amount such that the ratio of inhibitor composition 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. emulsion paints and aqueous powder coatings for metallic substrates.
The aqeous surface-coating composition may be, e.g. a paint such as a styrene-acrylic copolmyer emulsion paint, a resin, latex, or other aqueous based polymer surface-coating systems, to coat a metal substrate. The inhibitor composition used according to the invention may be employed to prevent flash rusting of the metal substrate duringapplication of the surface coating and to prevent subsequent corrosion during use of the coated metal.
In aqueous surface-coating compositions treated by the method of the invention the inhibitor composition 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 formula I, include the following:
Phenols, and alkyl- and halogenated phenols, for example, pentachlorophenol, o-phenylphenol, o-phenoxyphenol and chlorinated o-phenoxyphenol, and salicylanilides, 1~39536 diamines, triazines and organometallic compounds such as organomercury compounds and organotin compounds.
Examples of emlllsifiçrs for aqueous surface coatings include alkyl sulfates, alkyl sulfonates, ether-alcohol sulphonates, di-n-alkyl sulphosumates and polyoxyethylen nonylphenyl ethers.
Examples of pigments which may be used in these aqueous systems, in addition to the compound of formula I, include titanium dioxide, zinc chromate, iron oxide and organic pigments such as the phthalocyanines.
As already indicated compounds of formula I also function as dispersing agents and/or antifoulants towards common deposits, e.g. iron oxides and/or iron salts, calcium and magnesium deposits, e.g. their carbonates, sulphates, oxalates and phosphates, and silt, alumina, silicates and clays found in such waters.
In particular, the method of the present invention may be applied to disperse deposits in an aqueous system containing S to 1500 ppm by weight of calcium ion as well as suspended solids. This aspect of the present invention finds particular use in the china clay industry in which it is important to obtain slurries which will not appreciably separate out during transportation from the clay pits to the user. At high concentrations of suspended solids in these slurries, the compounds of formula I have been found to disperse china clay and to be of value as "in-process" dispersants and as grinding aids.
The following Examples further illustrate the present invention. All parts and percentages are by weight, unless stated otherwise.
Example 1: To 12.1 parts by weight of di-ethylphosphite are added, separately, 70 parts by weight of diethyl but-1-en-2,4-dicarboxylate and 5.75 parts by weight of di-tert-butyl-peroxide, dropwise, over 3 hours, with stirring at 140~C. The temperature is maintained at 140~C for a further 2 hours after the additions are complete. Unreacted di-ethyl-phosphite is removed by distillation under reduced pressure up to 200~/130 Pa and the residual liquid is suspended in 400 parts by weight of concentrated hydrochloric acid, and the mixture heated under reflux conditions for 18 hours.
The resulting solution is evaporated to dryness under reduced pressure at 100~C/1600 Pa 133~36 to give 53 parts by weight of a solid polymer having a molecular weight of 1430.
The absence of phosphorous acid and the presence of the phosphonic acid telogen is proven be 31p nmr analysis (multiple signals at 28 ppm).
Example 2: Following the procedure described in Example 1, from 23 parts by weight of diethylphosphite, 52.7 parts by weight of di-methyl itaconate ad 5.3 parts by weight of di-tert-butyl-peroxide there are obtained 44.5 parts by weight of a polymer having a molecular weight of 590 and a 31p multiple spectrum around 25-30 ppm.
Example 3: Calcium carbonate (cooling water) threshold test Test Conditions Test temperature 70~C
Test duration 30 minutes Aeration rate 500 cc/min (per 100 ml) Calcium 150 ppm as Ca2+
Magnesium 45 ppm as Mg2+
Carbonate 51 ppm as co32-Bicarbonate 269 ppm as -HCO3 Test additive 1 ppm The test is designed to assess the ability of an additive to inhibit the precipitation of CaCO3. The water composition simulates cooling water and the high temprature represents the conditions which exist close to a heat exchanger. Air bubbling is used to increase the severity of the test conditions.
A volume of solution containing sodium carbonate and sodium bicarbonate is mixed with an equal volume of a solution containing calcium chloride and magnesium chloride which already contains the test additive. The resulting test solution, through which air is bubbled at a contant rate, is stored at 70~C for 30 minutes. After this tirrle, the solution is filtered and the calcium remaining in the filtrate is determined by EDTA titration.
Each test is carried out in duplicate, and the first test is a standard test which determines the actual Ca2+ concentration in the test.
13~36 titre of test-titre of blank % CaC03 inhibition = x 100 titre of standard-titre of blank The standard and blank titres are usually 15-16 ml and 5-6 ml, respectively.
The product of Example 1, at 1 ppm level of addition, gave a % CaC03 inhibition of 63.
Claims (15)
1. Compound having the formula I:
wherein M1, M2, M3, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal atom, ammonium or C1-C4alkyl ammonium, hydroxy C1-C4alkyl ammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium, bis(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonium or 2-hydroxy-3-p-nonylphenoxy propyl ammonium;
R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups and p is an integer.
wherein M1, M2, M3, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal atom, ammonium or C1-C4alkyl ammonium, hydroxy C1-C4alkyl ammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium, bis(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonium or 2-hydroxy-3-p-nonylphenoxy propyl ammonium;
R1 is C1-C4alkyl substituted by one or more hydroxy or carboxyl groups and p is an integer.
2. Compound according to claim 1 wherein p is an integer within the range of from 1 to 99.
3. Compound according to claim 1 wherein p is an integer within the range from 1 to 20.
4. Compound according to claim 1 wherein all three of M1, M2 and M3 are hydrogen, a monovalent or an equivalent of a polyvalent metal atom, ammonium or C1-C4alkyl ammonium, hydroxy C1-C4alkyl ammonium or 2-hydroxy-3-p-nonylphenoxy propyl ammonium ion.
5. Process for the production of a compound of formula I, as defined in claim 1, comprising reacting p+1 moles of a compound of formula II
CH2=C(R1)-CO2R3 II
and one mole of a compound having the formula III:
III
wherein p and R1 have the significance given in claim 1, and R3, R4 and R5, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal ion, ammonium or C1-C4alkyl ammonium, hydroxy C1-C4alkyl ammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium, bis(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonium or 2-hydroxy-3-p-nonylphenoxy propyl ammonium ion.
CH2=C(R1)-CO2R3 II
and one mole of a compound having the formula III:
III
wherein p and R1 have the significance given in claim 1, and R3, R4 and R5, independently, are hydrogen, C1-C4alkyl, phenyl, a monovalent or an equivalent of a polyvalent metal ion, ammonium or C1-C4alkyl ammonium, hydroxy C1-C4alkyl ammonium, bis(2-hydroxyethyl) ammonium, tris(2-hydroxyethyl) ammonium, bis(2-hydroxyethyl)-2-hydroxy-3-p-nonylphenoxy propyl ammonium or 2-hydroxy-3-p-nonylphenoxy propyl ammonium ion.
6. Process according to claim 5 whereln the process is effected in the presence of a free radical initiator.
7. Method of treating an aqueous system comprising adding to the system a compound of formula I as defined in claim 1.
8. Method according to claim 7 wherein the system is treated to provide a corrosion-inhibiting treatment, or a corrosion-inhibiting with simultaneous scale-inhibiting treatments, and the compound of formula I is added in amount of from 0.1 to 50,000 ppm by weight, based on the weight of the aqueous system.
9. Method according to claim 8 wherein the compound of formula I is added in amount of 1 to 500 ppm by weight, based on the aqueous system.
10. Method according to claim 7 wherein the system is treated to provide solely an anti-scale treatment and the compound of formula I is added in amount of 1 to 200 ppm by weight, based on the aqueous system.
11. Method according to claim 10 wherein the compound of formula I is added in amount of 1 to 30 ppm by weight, based on the aqueous system.
12. Method according to claim 7 wherein the system is treated to provide a dispersant/antifoulant treatment and the amount of compound of formula I added is from 1 to 200 ppm by weight based on the aqueous system.
13. Method according to claim 12 wherein the compound of formula I is added in amount of 1 to 30 ppm by weight, based on the aqueous system.
14. Method according to claim 7 wherein the compound of formula I is used in conjunction with one or more of polymaleic or polyacrylic acid or their copolymers, or substituted copolymers; hydroxyphosphonoacetic acid, hydroxyethyl dephosphonic acid; 2-phosphono-butane-1,2,4-tricarboxylic acid; a triazole; a molybdate; or a nitrite.
15. A method according to claim 14 wherein said triazole is a tolutriazole.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8822144.5 | 1988-09-21 | ||
| GB888822144A GB8822144D0 (en) | 1988-09-21 | 1988-09-21 | Compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339536C true CA1339536C (en) | 1997-11-11 |
Family
ID=10643973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000611895A Expired - Fee Related CA1339536C (en) | 1988-09-21 | 1989-09-19 | Telomeric compound |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5073299A (en) |
| EP (1) | EP0360747B1 (en) |
| JP (1) | JP2939754B2 (en) |
| AU (1) | AU615800B2 (en) |
| BR (1) | BR8904716A (en) |
| CA (1) | CA1339536C (en) |
| DE (1) | DE68924632T2 (en) |
| GB (1) | GB8822144D0 (en) |
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| US5629396A (en) * | 1989-01-17 | 1997-05-13 | The Dow Chemical Company | Latex containing oxazoline for industrial coatings |
| GB9024470D0 (en) * | 1990-11-10 | 1991-01-02 | Ciba Geigy Ag | Corrision inhibition |
| US5386038A (en) * | 1990-12-18 | 1995-01-31 | Albright & Wilson Limited | Water treatment agent |
| CA2057822C (en) * | 1990-12-18 | 1998-04-21 | Keith Philip Davis | Water treatment agent |
| US5256746A (en) * | 1991-04-25 | 1993-10-26 | Rohm And Haas Company | Low molecular weight monoalkyl substituted phosphinate and phosphonate copolymers |
| US5681479A (en) * | 1991-05-31 | 1997-10-28 | Fmc Corporation (Uk ) Limited | Phosphonic cotelomers and method of use |
| GB9111704D0 (en) * | 1991-05-31 | 1991-07-24 | Ciba Geigy | Telomers |
| US6063288A (en) * | 1998-06-30 | 2000-05-16 | Betzdearborn Inc. | Inhibition of silica and silicate deposition using imidazolines |
| US6077440A (en) * | 1998-06-30 | 2000-06-20 | Betzdearborn Inc. | Inhibition of silica and silicate deposition |
| US6585933B1 (en) | 1999-05-03 | 2003-07-01 | Betzdearborn, Inc. | Method and composition for inhibiting corrosion in aqueous systems |
| US6841198B2 (en) | 2001-10-18 | 2005-01-11 | Strike Investments, Llc | Durable press treatment of fabric |
| US7018422B2 (en) | 2001-10-18 | 2006-03-28 | Robb Richard Gardner | Shrink resistant and wrinkle free textiles |
| US7169742B2 (en) | 2001-10-18 | 2007-01-30 | The Procter & Gamble Company | Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents |
| US6989035B2 (en) | 2001-10-18 | 2006-01-24 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
| US7008457B2 (en) | 2001-10-18 | 2006-03-07 | Mark Robert Sivik | Textile finishing composition and methods for using same |
| US7144431B2 (en) | 2001-10-18 | 2006-12-05 | The Procter & Gamble Company | Textile finishing composition and methods for using same |
| US7727420B2 (en) * | 2005-05-17 | 2010-06-01 | Ppt Research | Corrosion inhibiting compositions |
| US8025840B2 (en) * | 2008-10-31 | 2011-09-27 | General Electric Company | Compositions and methods for inhibiting corrosion in aqueous media |
| US8021607B2 (en) * | 2008-10-31 | 2011-09-20 | General Electric Company | Methods for inhibiting corrosion in aqueous media |
| MX2011010889A (en) * | 2009-04-21 | 2011-11-02 | Ecolab Usa Inc | Catalytic water treatment method and apparatus. |
| US9193610B2 (en) | 2011-08-10 | 2015-11-24 | Ecolab USA, Inc. | Synergistic interaction of weak cation exchange resin and magnesium oxide |
| CN102898574B (en) * | 2012-10-25 | 2014-06-25 | 南京大地冷冻食品有限公司 | Preparation method of novel environment-friendly high-efficiency detergent |
| EP2813524A1 (en) * | 2013-06-10 | 2014-12-17 | Basf Se | Phosphorylated polymers |
| EP2876117B1 (en) | 2013-11-22 | 2019-12-25 | Rohm and Haas Company | (Meth)acrylic propene co-polymers and a method for their production |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA509034A (en) * | 1955-01-11 | Dominion Rubber Company | Organo-phosphorus compounds and process of making same | |
| NL76613C (en) * | 1948-07-01 | |||
| GB694772A (en) * | 1948-07-10 | 1953-07-29 | Us Rubber Co | Improvements in phosphonic acid esters |
| GB660169A (en) * | 1948-07-10 | 1951-10-31 | Us Rubber Co | Improvements in organo-phosphorus compounds and process of making same |
| US3048613A (en) * | 1948-07-10 | 1962-08-07 | Us Rubber Co | Organo-phosphorus compounds and process of making same |
| US4159946A (en) * | 1974-06-11 | 1979-07-03 | 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 |
| US4127483A (en) * | 1974-06-11 | 1978-11-28 | Ciba Geigy (Uk) Limited | Treatment of aqueous systems |
| JPS5998150A (en) * | 1982-11-26 | 1984-06-06 | Adeka Argus Chem Co Ltd | Halogen-containing resin composition |
| JPS6011566A (en) * | 1983-06-30 | 1985-01-21 | Pentel Kk | Ball point water ink |
-
1988
- 1988-09-21 GB GB888822144A patent/GB8822144D0/en active Pending
-
1989
- 1989-09-12 EP EP89810681A patent/EP0360747B1/en not_active Expired - Lifetime
- 1989-09-12 DE DE68924632T patent/DE68924632T2/en not_active Expired - Fee Related
- 1989-09-19 CA CA000611895A patent/CA1339536C/en not_active Expired - Fee Related
- 1989-09-19 US US07/409,225 patent/US5073299A/en not_active Expired - Lifetime
- 1989-09-20 BR BR898904716A patent/BR8904716A/en unknown
- 1989-09-21 AU AU41719/89A patent/AU615800B2/en not_active Ceased
- 1989-09-21 JP JP1246257A patent/JP2939754B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB8822144D0 (en) | 1988-10-26 |
| DE68924632D1 (en) | 1995-11-30 |
| EP0360747A3 (en) | 1991-05-02 |
| EP0360747B1 (en) | 1995-10-25 |
| JPH02140207A (en) | 1990-05-29 |
| US5073299A (en) | 1991-12-17 |
| AU4171989A (en) | 1990-03-29 |
| DE68924632T2 (en) | 1996-06-05 |
| EP0360747A2 (en) | 1990-03-28 |
| AU615800B2 (en) | 1991-10-10 |
| JP2939754B2 (en) | 1999-08-25 |
| BR8904716A (en) | 1990-05-01 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |