US 5,055,230 AGrant
Corrosion Inhibiting Compositions
Issue Date:1991-10-08
•19 Claims
Abstract
A composition, in contact with a corrodable metal surface, comprising: a) an aqueous-based or oil-based system; and b) as an inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I or II: ##STR1## in which R is C.sub.4 -C.sub.20 alkyl, C.sub.4 -C.sub.20 alkyl interrupted by one or more oxygen atoms, C.sub.4 -C.sub.20 alkenyl, C.sub.6 -C.sub.10 aryl, C.sub.7 -C.sub.15 alkaryl, C.sub.7 -C.sub.15 aralkyl or C.sub.5 -C.sub.12 cycloalkyl; R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is methyl or, preferably, hydrogen; M is hydrogen, a metal ion, ammonium or substituted ammonium ion; a is 0 or 1; b is 0 or an integer from 1 to 6, preferably 0, 1, 2 or 3 especially 0 or 1; and c is an integer from 1 to 6; and/or at least one compound having the formula II: ##STR2## in which R, R.sup.3 and a are as defined above.
Metadata
Assignee
- Ciba-Geigy Corporation
Inventors
- Brian G. Clubley
- David C. Parker
Application Information
Application Number:US 524675&
Filing Date:1990-05-15
Priority Date:1987-07-14
Art Unit:221
Classifications
IPC:
C23F 1110
Field of Search:
252562260422549396;389.1;389.6258741312;13;17274
Patent Drawings
This patent does not have any drawings.
Description
EXAMPLE 1
6-Decyl-1,4-dioxan-2-one
Sodium (0.25 moles) is stirred in 150 ml of dry toluene and dodecane-1,2-diol (0.25) is added dropwise at 40.degree. C. When addition is complete, the mixture is heated at reflux to dissolve the sodium. After cooling to room temperature, ethyl chloroacetate (0.32 moles) is added over 10 minutes.
The mixture is now refluxed for 12 hours, during which time a white precipitate is produced. After cooling, equal volumes of water and petroleum ether are added and the resultant mixture allowed to separate.
The organic layer is evaporated to dryness. The residue is taken up in petroleum ether and the white solid filtered off and discarded. Again the solvent is evaporated.
The residue is refluxed with 850 ml water containing 60 g of sodium hydroxide for 18 hours, before cooling and washing with a mixture of ether and petroleum spirit. The aqueous layer is then acidified to pH 1.5 using 98% sulphuric acid. The product is taken up into 1000 ml of ether. After drying, the solvent is evaporated to yield 33% of the title compound which has satisfactory spectral properties (i.r. and n.m.r.).
EXAMPLES 2 TO 6
Using the method of Example 1 above, the following compounds are also synthesized;
EXAMPLE 2
6-Butyl-1,4-dioxan-2-one
EXAMPLE 3
6-Hexyl-1,4-dioxan-2-one
EXAMPLE 4
6-Butoxymethyl-1,4-dioxan-2-one
EXAMPLE 5
6-Isooctylmethyl-1,4-dioxan-2-one
EXAMPLE 6
6-Phenoxymethyl-1,4-dioxan-2-one
All isolated compounds having satisfactory spectral details (i.r. and n.m.r.).
EXAMPLES 7 TO 11
The same method of Example 1 is again employed but replacing the ethyl chloroacetate with ethylchloropropionate to prepare
EXAMPLE 7
3-(2'-hydroxy)octyloxypropanoic acid
EXAMPLE 8
3-(2'-hydroxy)decyloxypropanoic acid
EXAMPLE 9
3-(2'-hydroxy)dodecyloxypropanoic acid
EXAMPLE 10
3-(3'-isooctyloxy-2'-hydroxy)propoxypropanoic acid
Again all isolated compounds having satisfactory spectral details.
EXAMPLE 11
6-Octyl-1,4-dioxan-2-one
Powdered decane-1,2-diol (0.25 moles) is stirred at room temperature and very well powdered sodium hydroxide (0.25 moles) is added in portions. Gentle heating of the mixture to 55.degree. C. gives a viscous yellow paste. Sodium chloroacetate (0.25 moles) is now added in portions over 10 minutes. The white mobile paste produced is stirred at 70.degree.-60.degree. C. for 1.75 h. After cooling to 20.degree. C., 100 ml of petroleum ether is added followed by water. After separation of phases (aided by acetone) the aqueous phase is run off and acidified to pH 1.5 using 98% sulphuric acid. The oil produced is taken up into 2.times.375 ml diethyl ether which is then dried and evaporated to leave the title product as a clear oil (63%).
EXAMPLE 12
6-Decyl-1,4-dioxan-2-one
Sodium (0.08 moles) is added in small pieces to ethylene glycol (dried over 4A mol. sieves-7.2 moles) and the mixture heated to 130.degree. C. After complete solution of the sodium, dodecene-1,2-oxide (0.66 moles) is added over 15 minutes. After a further 1 hour at 130.degree. C. the mixture is heated at 150.degree. C. for 18 hours.
Excess ethylene glycol is removed in vacuo (water pump). The resultant residue is dissolved in 600 ml dichloromethane and washed with water. The organic phase is dried and evaporated.
A portion of the resultant brown liquid (0.01 moles) is stirred in 50 ml water containing 5 ml dioxan and 0.02 moles of sodium hydroxide, together with 0.5 g of a 5% platinum on charcoal catalyst. Air is forced over the reaction mixture, which is heated at 70.degree. C. for 12 hours.
The catalyst is removed by filtration and the aqueous solution acidified. The product is extracted into ether which is dried and evaporated to yield the product as a brown oil which crystallises to a buff solid. Shaking the product with 60-80 petroleum ether, followed y filtration, gives the product as a white crystalline solid (m.p. 52.degree.-52.5.degree. C.) with satisfactory spectra (i.r., n.m.r.).
EXAMPLE 13
6-Decyloxymethyl-1,4-dioxan-2-one
43 g of ethylene glycol is stirred under nitrogen at 20.degree. C. and 0.16 g of sodium added. The mixture is heated at 100.degree. C. until all the sodium dissolves, at which time 15 g of decylglycidyl ether is added over 0.5 hours. The resulting mixture is then stirred at 130.degree. C. for 17 hours before cooling and adding 0.4 g of glacial acetic acid. The excess ethylene glycol is next removed in vacuo (water pump) to leave a residue which is not isolated.
To this residue is added 200 ml of distilled water and the resulting inhomogeneous mixture heated to 70.degree. C. and 0.8 g of catalyst (5% Pd on charcoal) added. Air is drawn over the reactants and the pH maintained between pH 10 and pH 10.5 by titrating amount of sodium hydroxide solution. When the reaction has consumed the theoretical amount of sodium hydroxide, it is cooled and filtered. After washing with ether the aqueous phase is acidified to pH 1.5 using 98% sulphuric acid. The oil produced is extracted into ether which is then dried and evaporated to leave the product as an oil (30%) which has satisfactory spectral properties (i.r., n.m.r.).
EXAMPLE 14
6-C.sub.9 -C.sub.11 Alkoxymethyl-1,4-dioxan-2-one
Using the method described in Example 13, a glycidyl ether derived from Linevol 911 (a mixed C.sub.9 -C.sub.11 alcohol sold by Shell) is reacted with ethylene glycol and the title product was obtained containing a small amount of lactone--in 64% yield with satisfactory spectral properties (i.r.+n.m.r.).
In this preparation the catalytic oxidation was performed using oxygen rather than air as in Example 13.
EXAMPLE 15
6-C.sub.12 -C.sub.13 Alkyloxymethyl-1,4-dioxan-2-one
Sodium (0.83 g) is dissolved in ethylene glycol (223.8 g) and the glycidyl ether derived from Dobanol 23 (a mixture of mainly linear C.sub.12 and C.sub.13 alcohols, produced by Shell) (90.0 g) is added dropwise over 1 hour at 130.degree.-150.degree. C. under an atmosphere of nitrogen. The mixture is then reacted at this temperature for 11 hours. Acetic acid (2.16 g) is added, after cooling, and the ethylene glycol is removed by distillation. The residue is purified by distillation under high vacuum.
50 g of the product so obtained is dissolved in 500 ml of dichloromethane, and 16 ml of a 0.1M solution of tetramethyl piperidyl nitroxyl radical in dichloromethane, together with 1.9 g of potassium bromide dissolved in 20 ml of water are added.
This mixture is stirred rapidly whilst 500 ml of a 7% solution of sodium hypochlorite, saturated with sodium bicarbonate, are added, dropwise, with cooling, such that the temperature remains below 5.degree. C. After completion of the addition, the mixture is stirred for a further 10 minutes. Excess oxidant is decomposed with aqueous sodium sulphate, and the mixture is then acidified with a 7% HCl solution.
After separation of the phases, the organic phase is run off, washed with water and dried. Evaporation of the solvent in vacuo gives the title dioxan-2-one as an orange mobile liquid (mass recovery=96%).
.sup.1 H nmr: .delta.=4.5 (1H,m) CHOCO, 4.2 (2H,s OCH.sub.2 CO), 4.0-3.2 (6H, m CH.sub.2 O) 1.7-0.9 (alkyl chain).
I.r.: 2900 cm.sup.-1 (C--H), 1750 cm.sup.-1 (C.dbd.O).
EXAMPLES 16-22
Using the method described in Example 15 and starting from the appropriate glycidyl ethers described below the following compounds are prepared.
EXAMPLE 16
6-Dodecyloxymethyl-1,4-dioxan-2-one
Prepared from the glycidyl ether of dodecanol.
EXAMPLE 17
6-Tridecyloxymethyl-1,4-dioxan-2-one
Prepared from the glycidyl ether of tridecanol.
EXAMPLE 18
6-Tetradecyloxymethyl-1,4-dioxan-2-one
Prepared from the glycidyl ether of tetradecanol.
EXAMPLE 19
6-Hexadecyloxymethyl-1,4-dioxan-2-one
Prepared from the glycidyl ether of hexadecanol.
EXAMPLE 20
6-C.sub.14 -C.sub.15 -alkyloxymethyl-1,4-dioxan-2-one
Prepared from the glycidyl ether of Dobanol 45, a mixture of C.sub.14 and C.sub.15 alcohols commercially available from Shell.
EXAMPLE 21
6-C.sub.12 -C.sub.15 -alkyloxymethyl-1,4-dioxan-2-one
Prepared from Azepoxy 8, a commercially available mixture of C.sub.12 and C.sub.14 glycidyl ethers supplied by the AZS corporation.
EXAMPLE 22
6-C.sub.12 -C.sub.15 -alkyloxymethyl-1,4-dioxan-2-one
Prepared from Epoxy 8, a commercially available mixture of C.sub.12 and C.sub.14 glycidyl ethers supplied by Proctor and Gamble.
EXAMPLE 23
3-(3'-alkoxy-2'-hydroxy)propoxy propanoic acid
Using the method of Example 14, but replacing ethylene glycol with 1,3-propane diol, the title product is obtained in 23% yield, again with satisfactory spectral properties (i.r.+n.n.r.).
EXAMPLE 24
4-(3'-alkoxy-2'-hydroxy)propoxybutanoic acid
Using the method of Example 14, but replacing ethylene glycol with 1,4-butone diol, the title product is obtained in good yield and with satisfactory spectral properties (i.r.+n.m.r.).
EXAMPLE 25
4-(3'-alkoxy-2'-hydroxy)propoxybutanoic acid-sodium salt
The final aqueous solution in Example 17, before acidification, is found--by drying--to be a 7.3% w/w solution of the title compound sodium salt.
EXAMPLE 26 AND 27
Using the procedures of Examples 13-14 and 24-25 the following compounds have also been synthesized
EXAMPLE 26
2-(3'-C.sub.9 -C.sub.11 alkoxy-2'-hydroxy)propoxyacetic acid, sodium salt
EXAMPLE 27
2-(3'-paranonylphenoxy-2'-hydroxy)propoxyacetic acid.
EXAMPLE 28 ##STR15##
Using the same procedure as in Example 13, dodecene-1,2-oxide is reacted with diethylene glycol. In this case the intermediate product is distilled to give C.sub.10 H.sub.21 CH(OH)CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH as a white crystalline solid (b.p. 120.degree. C./0.2 mm Hg). This diol is then oxidised as in Example 16 to produce the above compound in good yield with satisfactory spectral details (i.r.+n.m.r.) as a yellow oil.
EXAMPLE 29 ##STR16##
The title compound is prepared using the procedure described in Example 28, but replacing the diethylene glycol with triethyleneglycol.
EXAMPLE 30 ##STR17##
The title compound is prepared by the method of Example 21 using the glycidyl ether derived from Dobanol 23 (a mixed C.sub.12 -C.sub.13 alcohol from Shell).
EXAMPLE 31 ##STR18##
Using the method of Example 21, reacting the glycidyl ether derived from Dobanol 23 with triethylene glycol, the title compound is prepared. Dissolving the compounds of Examples 1-24 in sodium hydroxide solution gives rise to the sodium salts of the compounds.
EXAMPLE 32 ##STR19##
Azepoxy 8, (the glycidyl ether described in Example 21 above) (28 ml) is added dropwise over 15 minutes to 28 ml of 20% HCl at reflux under nitrogen. After addition is complete reflux is maintained for a further 15 minutes. The mixture is cooled and allowed to separate.
EXAMPLES 33 TO 36
Corrosion inhibitor activity of compounds of formula I or II is demonstrated in the Aerated Solution Bottle Test using standard corrosive waters have the following compositions:
In the Table, "pA" denotes phenol alkalinity in ppm as CaCO.sub.3 ; "TA" denotes total alkalinity in ppm as CaCO.sub.3 ; and "TH" denotes total hardness in ppm as CaCO.sub.3.
Mild steel coupons measuring 5 cms by 2.5 cms are scrubbed with pumice, immersed for one minute in hydrochloric acid and then rinsed, dried and weighed.
200 ppm of test additive as a sodium salt is dissolved in 200 ml of standard corrosive water. Two steel coupons are suspended in the solution, and the whole stored in a closed bottle in a thermostat at 40.degree. C. During the storage period, air is passed into the solution at 500 ml/minute, the passage of the air being screened from the steel coupon; any water losses by evaporation are replaced with distilled water.
After 64 hours, the steel 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 specimen in the test water in the absence of any potential corrosion inhibitor, is carried out with each series of tests. The corrosion rates are calculated in milligrams of weight loss/sq. decimeter/day (m.d.d.).
The results obtained in a series of tests are set out in Table I.
EXAMPLES 37 AND 42
The corrosion inhibitor activity of the product of Examples 14 and 15 is examined in the Rotating Coupon Test using the following standard corrosive waters:
In a 1 liter reservoir of one of the test waters, two-precleaned and pre-weighed mild steel coupons are rotated at a coupon velocity of 61 cms per second. The test is conducted over 48 hours in oxygenated water at 40.degree. C. using 20 ppm of the appropriate concentration of corrosion inhibitor.
The coupons are removed, cleaned and the corrosion rates are determined as determined as described in Examples 33 to 36. The results are shown in Table II below:
EXAMPLE 43
The corrosion inhibitor activity of the product of Example 1 is examined in a recirculating pilot cooling water rig system using the standard corrosive water 5M as described in Examples 33 to 36.
The recirculating rig used consists of a 20 liter reservoir of the standard corrosive which is recirculated over two precleaned and preweighed heat exchangers (H1 and H2) and over precleaned and preweighed metal coupons. The reservoir temperature is kept at 40.degree. C. and a high level (80 ppm) inhibitor treatment for one day before continuing with maintenance level (20 ppm) for a further six days.
The heat exchangers and coupons are then cleaned and the corrosion rates are determined in the manner described in Examples 33 to 36. The results are summarised in Table III.
EXAMPLES 44 TO 65
The use of the products of this invention, when used in conjunction with other additives, is exemplified by the results shown in Table IV. A product of this invention (COMPONENT A--described in Example 15) is tested in conjunction with a second additive (COMPONENT B) at the dose levels shown. The corresponding result for COMPONENT B in the absence of COMPONENT A is shown for comparison purposes. The test conditions are those of the Rotating Coupon Test described for Examples 37 to 44 above, and all relate to the 150 Ca water.
EXAMPLE 67
As an Example of a further use of compounds in this invention, the product of Example 15, in its cyclised form (that is, as shown by formula II) was dissolved in a mineral oil to produce a 200 ppm solution. The corrosion inhibitor efficacy of this material was tested in the D665B rotating spindle test. The result is shown below.
Claims
We claim:
1. A process for inhibiting the corrosion of a metal surface comprising: contacting the metal surface with a composition comprising: a) an aqueous-based system; and b) as an inhibitor for protecting the metal surface against corrosion, at least one compound having the formula I or II: ##STR20## in which R is C.sub.4 -C.sub.20 alkyl, C.sub.4 -C.sub.20 alkyl interrupted by one or more oxygen atoms, C.sub.4 -C.sub.20 alkenyl, C.sub.6 -C.sub.20 aryl, C.sub.7 -C.sub.15 alkaryl, C.sub.7 -C.sub.15 aralkyl or C.sub.5 -C.sub.12 cycloalkyl; R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is methyl or hydrogen; M is hydrogen, a metal ion, ammonium or substituted ammonium ion; a is 0 or 1; b is 0 or an integer from 1 to 6; and c is an integer from 1 to 6.
2. A process according to claim 1 in which the metal surface is a ferrous metal surface.
3. A process according to claim 1 in which R.sup.1, R.sup.2 and R.sup.3 are hydrogen.
4. A process according to claim 1 in which b is 0, 1, 2 or 3.
5. A process according to claim 4 in which b is 0 or 1.
6. A process according to claim 1 in which c is 1, 2 or 3.
7. A process according to claim 1, wherein R is of straight-chain and has 6 to 16 carbon atoms.
8. A process according to claim 7, wherein R is of straight-chain and has 8 to 15 carbon atoms.
9. A process according to claim 8, wherein R is of straight-chain and has 12 to 15 carbon atoms.
10. A process according to claim 1, in which R is C.sub.6 -C.sub.16 alkyl, a is 0 or b is 0, 1, 1, 2 b is 0, 1, or 3 and c is 1, 2 or 3.
11. A process according to claim 10 in which R is C.sub.8 -C.sub.15 alkyl, a is 0 or 1, b is 0 or 1 and c is 1, 2 or 3.
12. A process according to claim 11, wherein R is C.sub.13 -C.sub.15 alkyl, a is 1, b is 0 and c is 1.
13. A process according to claim 1 in which M is hydrogen, sodium or potassium, magnesium or calcium, bis(2-hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium or bis(2-hydroxyethyl)-(2-hydroxy-3-p-nonylphenoxy)propylammonium.
14. A process according to claim 1, wherein the amount of the compound of formula I or II present is 0.0001 to 5% by weight, based on the total amount of the aqueous-based system.
15. A process according to claim 1 further comprising one or more antioxidants, metal deactivators, corrosion inhibitors, rust inhibitors, complexing agents, precipitation inhibitors, biocides, buffering agents or antifoams.
16. A process according to claim 1 wherein the compound of formula I or II has been produced by reacting a diol of the formula VI: ##STR21## with an .omega.-halocarboxylic ester of the formula VII: ##STR22## to obtain a compound of formula VIII: ##STR23## and/or a compound of formula X ##STR24## wherein R is C.sub.4 -C.sub.20 alkyl, C.sub.4 -C.sub.20 alkyl interrupted by one or more oxygen atoms, C.sub.4 -C.sub.20 alkenyl, C.sub.6 -C.sub.10 aryl, C.sub.7 -C.sub.15 alkaryl, C.sub.7 -C.sub.15 aralkyl or C.sub.5 -C.sub.12 cycloalkyl; R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is methyl or hydrogen; M is hydrogen, metal ion, ammonium or substituted ammonium ion; a is 0 or 1; b is 0 or an integer from 1 to 6; and c is an integer from 1 to 6 X is a halogen and R.sup.4 is a hydrocarbon residue and hydrolyzing the compound of formula VIII and/or X, to produce the corresponding compound of the formula I or II.
17. A process according to claim 1 wherein the compound of formula I or II has been produced by reacting a diol of the formula VI: ##STR25## with an .omega.-halo acid or salt of formula IX: ##STR26## in the presence of an appropriate amount of base, to produce a compound of formula I or II directly, or in combination with a compound of formula XI: ##STR27## wherein R is C.sub.4 -C.sub.20 alkyl, C.sub.4 -C.sub.20 alkyl interrupted by one or more oxygen atoms, C.sub.4 -C.sub.20 alkenyl, C.sub.6 -C.sub.18 aryl, C.sub.7 -C.sub.15 alkaryl, C.sub.7 -C.sub.15 aralkyl or C.sub.5 -C.sub.12 cycloalkyl; R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is methyl or hydrogen; M is hydrogen, metal ion, ammonium or substituted ammonium ion; a is 0 or 1; b is 0 or an integer from 1 to 6; and c is an interger from 1 to 6 X is a halogen and R.sup.5 is hydrogen or a metal ion,
18. A process according to claim 1 wherein the compound of formula I in which R.sup.3 is H and c is 2 has been obtained by reacting a diol of the formula VI: ##STR28## with acrylic acid or its sodium salt, in the presence of an appropriate amount of base, wherein R is C.sub.4 -C.sub.20 alkyl, C.sub.4 -C.sub.20 alkyl interrupted by one or more oxygen atoms, C.sub.4 -C.sub.20 alkenyl, C.sub.6 -C.sub.10 aryl, C.sub.7 -C.sub.15 alkaryl, C.sub.7 -C.sub.15 aralkyl or C.sub.5 -C.sub.12 cycloalkyl; R.sup.1 and R.sup.2 are the same or different and each is methyl or hydrogen; a is 0 or 1; b is 0 or an integer from 1 to 6.
19. A process according to claim 1 wherein component b) is the inhibitor of formula II.
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