CA1051859A - Vapor space corrosion inhibited compositions - Google Patents
Vapor space corrosion inhibited compositionsInfo
- Publication number
- CA1051859A CA1051859A CA228,807A CA228807A CA1051859A CA 1051859 A CA1051859 A CA 1051859A CA 228807 A CA228807 A CA 228807A CA 1051859 A CA1051859 A CA 1051859A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- composition
- diethanolamide
- oil
- vapor space
- 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
Links
Abstract
VAPOR SPACE CORROSION INHIBITED COMPOSITIONS
(D#72,669-F) ABSTRACT
An inhibitor consisting of a mixture of at least one fatty acid amide and of at least one amine salt of a C8-C10 acid has been found to give synergistic vapor space rust inhibition with lubricating oils.
The total inhibitor concentration ranges from about 0.01 to about 5.00 weight percent basis lubricating oil weight with the fatty acid amide to acid amine salt ranging from 1:1 to 1:10.
-I-
(D#72,669-F) ABSTRACT
An inhibitor consisting of a mixture of at least one fatty acid amide and of at least one amine salt of a C8-C10 acid has been found to give synergistic vapor space rust inhibition with lubricating oils.
The total inhibitor concentration ranges from about 0.01 to about 5.00 weight percent basis lubricating oil weight with the fatty acid amide to acid amine salt ranging from 1:1 to 1:10.
-I-
Description
~,o5~859 BACKGROUND OF Tl~ ~NVENTIO~
Field of the Invention:
This invention relates to novel corrosion inhibiting compositions which have particular utility in preventing vapor space rust.
It has been observed that steani turbine lubricating oil systems frequent]y exhibit severe corrosion of the metal surfaces not normally submerged in the oil. This corrosion is normally called "vapor space rust". Such corrosion is observed in the oil sump and oil return lines of many steam turbines. This vapor space rusting is undesirable because the rust particles oreak loose from the metal surface and cause filter plugging and reduce oil flow. Undesirably, the ~st particles can reach the bearings, reduction gears, and governors thereby causing extensive damage and costly down ti~le. The use of vapor space rust inhibitors, which coat the metal surface and prevent rusting, o~fers a promis-ing solution to vapor phase rust inhibition proble~s.
DescriPtion of the Prior Art:
~ Some degree of vapor space rust inhibition has been obtained from suitable members of the following types of compounds: aliphatic and aromatic acids; primary, secondary and tertiary amines; amine salts of organic acids; and alkylolamir.es. U. S. Patent 2,775,560 covers the usa of aliphatic monocarboxyl-Lc acids containing from 8 to 10 carbon atoms as vapor space rust inhibitors in turbine oil formula-tions In the literature, combinations of normal carboxylic acids (C8 to C10) with selected low molecular weight aliphatic amines have been used as vapor space rust inhibitors. Up to now this combination of acids and amines has not been suggested in the patent literature as vapor space rust inhibitors.
SUMMARY OF THE INVENTION
In accordance with the invention there is provided a lubricating oil composition having improved vapor space corrosion properties comprising from 0.01 to 5.00 weight percent, basis oil of a mixture of at least one amine salt of a C8 - C10 aliphatic monocarboxylic acid together with at least one amide of diethanolamine and a fatty acid containing from 12 to 20 carbon atoms, the ratio of amide to acid amine salt being from about 1:1 to about 1:10, the balance, a major amount of a mineral oil. The ratio of fatty amide to acid-amine salt ranges from 1:1 to 1:10 with the preferred ratio being 1:2 to 1:6. Uniquely, only unsaturated acids are effective.
Of the acids mentioned above the straight-chain mono or diun-saturated monocarboxylic acids (C12-C20) are preferred for reacting with diethanolamine. Suitable amines include normal, branched and cyclic ali-phatic amines; primary, secondary, tertiary and saturated heterocyclic amines having twelve carbon atoms or less in the alkyl group or groups.
The acid part of the amine salt can be a C8, Cg or C10 acid.
E~
DISCLOSURE
SYNTHESIS OF TALL OIL ACID-DIETHANOLAMINE
Equimolar amounts of Tall Oil Acid and diethanol-amine were cut back with approximately 25% xylene, and the mixture was heated at reflux until the calculated quantity of water was recovered from the desired reactions. The reaction mixture was then stripped to a constant weight yielding the desired product.
The amide has the following structure:
.. .
R-C-N-CH2-CH2-OH , R=C17 mono and diunsaturated hydro-carbon.
SYNTHESIS OF DECANOIC ACID-t-BUTYLAMINE SALT
Equimolar amounts of the acid and t-butylamine were heated together, with 10~ methanol dilution, for 2 hours at 120-130F. The methanol solvent was then removed by nitrogen stripping at atmospheric pressure, yielding the decanoic acid-t-butylamine salt. Other decanoic acid-amine salts were prepared by a similar method. The amine salt has the following structure:
o R-C-O H3N-C4Hg, R CgHlg EXPERIMENTAL RESULTS
Table I shows results obtained with a combina-tion of a fatty acid amine and a fatty acid amine salt.
Each of the individual additives was first evaluated as vapor space inhibitors separately and then compared to combinations of additives. The total concentra-tion of additive(s) was the same in all cases, either 0.10 or 0.15 wt. ~.
The inhibited oil blends were evaluated in a modified version of the Hot Plate Reflux Rust Testl where ~he hot plate was replaced with a constant temperature cil bath. Metal specimen were composed of SA~ 1018 mild steel.
The specimen were polished using 240 grit abrasive and stored under precipitation naphtha until they were used.
After the test was completed, the specimen were rated according to the amount and type of rust present. The following ratings were used:
1. ASTM Publication, 65th. Annual Meeting, Symposium on Turbine Oils (1962).
NR - No rust T - Trace Rust, a few isolated pin points of rust L - Light Rust, several pin points of rust or small rust spots M - Moderate Rust, specimen covered with rust or large rust spots S - Severe Ru~t, specimen heavily rusted and pitted Blends containing the individual additives had unsatisfactory ratings in the test. However, the blend containing decanoic acid had a much better rating than blends containing the other individual additives. The addition of a small amount of the fatty amide to oil blends containing decanoic acid combined with either t-butylamine or tributyl-amine gave synergistic effects in inhibiting vapor space rust as shown by the explanatory data presented in Table I. It can be readily seen that the combination of any two of the three components will not provide equivalent vapor space rust protection to oil blends. In order to have the noted improvement in vapor space rust inhibition, an oil blend must contain the fatty amide, a fatty acid, and an aliphatic amine. The acid and amine should be reacted together prior to being used to form an acid - amine salt.
Further, it can be seen that only fatty amides prepared from unsaturated acids are effective. Both the amide prepared from hydrogenated Tall Oil Acid and the amide prepared from stearic acid had unsatisfactory ratings when added to oil blends containing octanoic acid combined with tributylamine. By contrast, the amide prepared from Tall Oil Acid had improved vapor space rust protection when added to oil blends containing octanoic acid combined with tributylamine as shown by the explanatory data presented in Table I.
TABLE I
VAPOR SPACE RUST TEST RESULTS OF INHIBITED TURBINE OILS
Additive Wt. ~ Additivel Rusting 2 20 Hrs/210~F
Tall Oil Acid-diethanol 0.10 S
amide (TOA-DEA) 0.15 insoluble Decampoc acid 0.10 T, L
0.15 2L
t-Butylamine 0.10 3S
0.15 2M,S
Tributylamine 0.10 S
0.15 S
Decanoic acid/t-butylamine Q.10 T, 2L
0.15 T, 2L
Decanoic acid/ 0.10 3S
tributylamine (DATA) 0.15 M, 2S
Decanoic acid/TOA-DEA 0.10 3M
0.15 3L
TQA-DEA/ DA tert BA 0.10 3NR
O.15 3NR
TOA-DEA/DATA 0.10 2T, L
0.15 2T, L
TOA-DEA/octanoic acid/
tributylamine (QATA) 0.15 2T, L
ToA-DEA3/oATA o.l5 L, M, S.
stearic acid-diethanolamide/
DATA 0.15 3S
lIn Turbine Oil qualified agalnst MIL-L-17331F specification.
2NR - No Rust, T-Trace, L-Light, M-Moderate, S-Severe. A
No Rust to trace rating was considered a passing result.
The numbers show the no. of tests run.
3Prepared from hydrogenated Tall Oil Acid.
105~859 Pairs of amides and acid salts which give substantially equivalent results as the pairs exemplified ~n Table I included the following:
Diethanolamidel Acid Amine Salt _ Tall Oil Acid-dlethanolamide Decanoic acid-isobutylamine Palmitic acld-diethanolamide Decanoic acid-n-butylamine Oleic acid-diethanolamide Decanoic acid-n-pentylamine Linoleic acid-diethanolamide Decanoic acid-n-hexylamine Decanoic acid-cyclohexylamine Decanoic acid-morphollne Decanoic acid-N-methylmorpholine A vapor space rust inhibitor composit~Qn can be formed by combining any one of the diethanolamideæ listed with any of the acid/amine salts listed.
20ctanoic acid and nonanoic acid may be used in place of decanoic acid in the cases listed below and combined with t-butylamine and tributylamine.
Other additives can be used in usual amounts with the lubricants to which the vapor phase corrosion inhi~itors of the invention are added. Such additlves lnclude extreme pressure agents, anti-clogging agents, ant$rust agen s, oxidation inhib$tors and the like.
The base oil for the addltives of this invention can be any mineral hydrocarbon oil but usually is a turbine oil, a hydraulic oil or a draw~ng oil.
Field of the Invention:
This invention relates to novel corrosion inhibiting compositions which have particular utility in preventing vapor space rust.
It has been observed that steani turbine lubricating oil systems frequent]y exhibit severe corrosion of the metal surfaces not normally submerged in the oil. This corrosion is normally called "vapor space rust". Such corrosion is observed in the oil sump and oil return lines of many steam turbines. This vapor space rusting is undesirable because the rust particles oreak loose from the metal surface and cause filter plugging and reduce oil flow. Undesirably, the ~st particles can reach the bearings, reduction gears, and governors thereby causing extensive damage and costly down ti~le. The use of vapor space rust inhibitors, which coat the metal surface and prevent rusting, o~fers a promis-ing solution to vapor phase rust inhibition proble~s.
DescriPtion of the Prior Art:
~ Some degree of vapor space rust inhibition has been obtained from suitable members of the following types of compounds: aliphatic and aromatic acids; primary, secondary and tertiary amines; amine salts of organic acids; and alkylolamir.es. U. S. Patent 2,775,560 covers the usa of aliphatic monocarboxyl-Lc acids containing from 8 to 10 carbon atoms as vapor space rust inhibitors in turbine oil formula-tions In the literature, combinations of normal carboxylic acids (C8 to C10) with selected low molecular weight aliphatic amines have been used as vapor space rust inhibitors. Up to now this combination of acids and amines has not been suggested in the patent literature as vapor space rust inhibitors.
SUMMARY OF THE INVENTION
In accordance with the invention there is provided a lubricating oil composition having improved vapor space corrosion properties comprising from 0.01 to 5.00 weight percent, basis oil of a mixture of at least one amine salt of a C8 - C10 aliphatic monocarboxylic acid together with at least one amide of diethanolamine and a fatty acid containing from 12 to 20 carbon atoms, the ratio of amide to acid amine salt being from about 1:1 to about 1:10, the balance, a major amount of a mineral oil. The ratio of fatty amide to acid-amine salt ranges from 1:1 to 1:10 with the preferred ratio being 1:2 to 1:6. Uniquely, only unsaturated acids are effective.
Of the acids mentioned above the straight-chain mono or diun-saturated monocarboxylic acids (C12-C20) are preferred for reacting with diethanolamine. Suitable amines include normal, branched and cyclic ali-phatic amines; primary, secondary, tertiary and saturated heterocyclic amines having twelve carbon atoms or less in the alkyl group or groups.
The acid part of the amine salt can be a C8, Cg or C10 acid.
E~
DISCLOSURE
SYNTHESIS OF TALL OIL ACID-DIETHANOLAMINE
Equimolar amounts of Tall Oil Acid and diethanol-amine were cut back with approximately 25% xylene, and the mixture was heated at reflux until the calculated quantity of water was recovered from the desired reactions. The reaction mixture was then stripped to a constant weight yielding the desired product.
The amide has the following structure:
.. .
R-C-N-CH2-CH2-OH , R=C17 mono and diunsaturated hydro-carbon.
SYNTHESIS OF DECANOIC ACID-t-BUTYLAMINE SALT
Equimolar amounts of the acid and t-butylamine were heated together, with 10~ methanol dilution, for 2 hours at 120-130F. The methanol solvent was then removed by nitrogen stripping at atmospheric pressure, yielding the decanoic acid-t-butylamine salt. Other decanoic acid-amine salts were prepared by a similar method. The amine salt has the following structure:
o R-C-O H3N-C4Hg, R CgHlg EXPERIMENTAL RESULTS
Table I shows results obtained with a combina-tion of a fatty acid amine and a fatty acid amine salt.
Each of the individual additives was first evaluated as vapor space inhibitors separately and then compared to combinations of additives. The total concentra-tion of additive(s) was the same in all cases, either 0.10 or 0.15 wt. ~.
The inhibited oil blends were evaluated in a modified version of the Hot Plate Reflux Rust Testl where ~he hot plate was replaced with a constant temperature cil bath. Metal specimen were composed of SA~ 1018 mild steel.
The specimen were polished using 240 grit abrasive and stored under precipitation naphtha until they were used.
After the test was completed, the specimen were rated according to the amount and type of rust present. The following ratings were used:
1. ASTM Publication, 65th. Annual Meeting, Symposium on Turbine Oils (1962).
NR - No rust T - Trace Rust, a few isolated pin points of rust L - Light Rust, several pin points of rust or small rust spots M - Moderate Rust, specimen covered with rust or large rust spots S - Severe Ru~t, specimen heavily rusted and pitted Blends containing the individual additives had unsatisfactory ratings in the test. However, the blend containing decanoic acid had a much better rating than blends containing the other individual additives. The addition of a small amount of the fatty amide to oil blends containing decanoic acid combined with either t-butylamine or tributyl-amine gave synergistic effects in inhibiting vapor space rust as shown by the explanatory data presented in Table I. It can be readily seen that the combination of any two of the three components will not provide equivalent vapor space rust protection to oil blends. In order to have the noted improvement in vapor space rust inhibition, an oil blend must contain the fatty amide, a fatty acid, and an aliphatic amine. The acid and amine should be reacted together prior to being used to form an acid - amine salt.
Further, it can be seen that only fatty amides prepared from unsaturated acids are effective. Both the amide prepared from hydrogenated Tall Oil Acid and the amide prepared from stearic acid had unsatisfactory ratings when added to oil blends containing octanoic acid combined with tributylamine. By contrast, the amide prepared from Tall Oil Acid had improved vapor space rust protection when added to oil blends containing octanoic acid combined with tributylamine as shown by the explanatory data presented in Table I.
TABLE I
VAPOR SPACE RUST TEST RESULTS OF INHIBITED TURBINE OILS
Additive Wt. ~ Additivel Rusting 2 20 Hrs/210~F
Tall Oil Acid-diethanol 0.10 S
amide (TOA-DEA) 0.15 insoluble Decampoc acid 0.10 T, L
0.15 2L
t-Butylamine 0.10 3S
0.15 2M,S
Tributylamine 0.10 S
0.15 S
Decanoic acid/t-butylamine Q.10 T, 2L
0.15 T, 2L
Decanoic acid/ 0.10 3S
tributylamine (DATA) 0.15 M, 2S
Decanoic acid/TOA-DEA 0.10 3M
0.15 3L
TQA-DEA/ DA tert BA 0.10 3NR
O.15 3NR
TOA-DEA/DATA 0.10 2T, L
0.15 2T, L
TOA-DEA/octanoic acid/
tributylamine (QATA) 0.15 2T, L
ToA-DEA3/oATA o.l5 L, M, S.
stearic acid-diethanolamide/
DATA 0.15 3S
lIn Turbine Oil qualified agalnst MIL-L-17331F specification.
2NR - No Rust, T-Trace, L-Light, M-Moderate, S-Severe. A
No Rust to trace rating was considered a passing result.
The numbers show the no. of tests run.
3Prepared from hydrogenated Tall Oil Acid.
105~859 Pairs of amides and acid salts which give substantially equivalent results as the pairs exemplified ~n Table I included the following:
Diethanolamidel Acid Amine Salt _ Tall Oil Acid-dlethanolamide Decanoic acid-isobutylamine Palmitic acld-diethanolamide Decanoic acid-n-butylamine Oleic acid-diethanolamide Decanoic acid-n-pentylamine Linoleic acid-diethanolamide Decanoic acid-n-hexylamine Decanoic acid-cyclohexylamine Decanoic acid-morphollne Decanoic acid-N-methylmorpholine A vapor space rust inhibitor composit~Qn can be formed by combining any one of the diethanolamideæ listed with any of the acid/amine salts listed.
20ctanoic acid and nonanoic acid may be used in place of decanoic acid in the cases listed below and combined with t-butylamine and tributylamine.
Other additives can be used in usual amounts with the lubricants to which the vapor phase corrosion inhi~itors of the invention are added. Such additlves lnclude extreme pressure agents, anti-clogging agents, ant$rust agen s, oxidation inhib$tors and the like.
The base oil for the addltives of this invention can be any mineral hydrocarbon oil but usually is a turbine oil, a hydraulic oil or a draw~ng oil.
Claims (9)
1. A lubricating oil composition having improved vapor space corrosion properties comprising from 0.01 to 5.00 weight percent, basis oil of a mixture of at least one amine salt of a C8 - C10 aliphatic monocarboxylic acid together with at least one amide of diethanolamine and a fatty acid containing from 12 to 20 carbon atoms, the ratio of amide to acid amine salt being from about 1:1 to about 1:10, the balance, a major amount of a mineral oil.
2. The composition of Claim 1 wherein the concentration of said mixture ranges from 0.05 to 0.50 weight percent.
3. The composition of Claim 1 wherein said mixture consists of Tall Oil Acid - diethanolamide and decanoic acid-t-butylamine.
4. The composition of Claim 1 wherein said mixture consists of Tall Oil Acid-diethanolamide and decanoic acid-tributylamine.
5. The composition of Claim 1 wherein said mixture consists of Tall Oil Acid diethanolamide and decanoic acid-isobutylamine.
6. The combination of Claim 1 wherein said mixture consists of palmitic acid-diethanolamide and decanoic acid n-butylamine.
7. The combination of Claim 1 wherein said mixture of oleic acid-diethanolamide and decanoic acid-morpholine.
8. The composition of Claim 1 wherein said mixture consists of linoleic acid-diethanolamide and decanoic acid-n-pentylamine.
9. The composition of Claim 1 wherein said ratio of amide to acid amine salt ranges from about 1:2 to about 1:6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA228,807A CA1051859A (en) | 1975-06-09 | 1975-06-09 | Vapor space corrosion inhibited compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA228,807A CA1051859A (en) | 1975-06-09 | 1975-06-09 | Vapor space corrosion inhibited compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1051859A true CA1051859A (en) | 1979-04-03 |
Family
ID=4103273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA228,807A Expired CA1051859A (en) | 1975-06-09 | 1975-06-09 | Vapor space corrosion inhibited compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1051859A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018011058A1 (en) * | 2016-07-11 | 2018-01-18 | Byk-Chemie Gmbh | An organoclay composition and its use |
-
1975
- 1975-06-09 CA CA228,807A patent/CA1051859A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018011058A1 (en) * | 2016-07-11 | 2018-01-18 | Byk-Chemie Gmbh | An organoclay composition and its use |
| US11021643B2 (en) | 2016-07-11 | 2021-06-01 | Byk Usa, Inc. | Organoclay composition and its use |
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