Borated detergents and their lubricating applications

Patent metadata

Field	Value
Publication number	US-11939550-B2
Application number	US-202218061145-A
Country	US
Kind code	B2
Filing date	Dec 2, 2022
Priority date	Dec 9, 2021
Publication date	Mar 26, 2024
Grant date	Mar 26, 2024

Abstract

Disclosed herein is an overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both carbonate and borate moieties and exhibiting the following characteristics: a basicity index of at least 3.8; a ratio of soap content to mass % boron is greater than 55 mmol/kg; a soap content of at least 330 mmol/kg; a TBN, measured according to ASTM D2896, of at least 220 mg KOH/g; and a mass ratio of borate to carbonate from 0.75 to 6.0, wherein the alkaline earth metal comprises calcium and/or magnesium, and the hydrocarbyl substitution comprises 9 to 30 carbon atoms. Methods of making the boron-containing salicylate detergent, specifically to be package-stable, are also disclosed, as well as package-stable lubricant additive package concentrates and lubricating oil compositions containing same.

First claim

What is claimed is:

1. An overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both carbonate and borate moieties and exhibiting the following characteristics:
a basicity index of at least 3.8;
a ratio of soap content to mass % boron is greater than 55 mmol/kg;
a soap content of at least 330 mmol/kg and less than or equal to 500 mmol/kg;
a TBN, measured according to ASTM D2896, of at least 220 mg KOH/g; and
a mass ratio of borate to carbonate from 0.75 to 6.0,
wherein the alkaline earth metal comprises calcium and/or magnesium, and the hydrocarbyl substitution comprises 9 to 30 carbon atoms.

2. An overbased calcium salicylate detergent according to claim 1 , wherein all four of the following are satisfied:
the basicity index is not greater than 9.0;
the ratio of soap content to mass % boron is less than 300 mmol/kg;
the TBN, measured according to ASTM D2896, is at most 500 mg KOH/g; and
the hydrocarbyl substitution comprises a C 14 to C 24 alkyl or alkenyl moiety.

3. An overbased calcium salicylate detergent according to claim 1 , which exhibits a boron content, according to ASTM D4951, of at least 3.2% by mass.

4. An overbased calcium salicylate detergent according to claim 1 , wherein the mass ratio of borate to carbonate is from 1.0 to 5.0.

5. An overbased calcium salicylate detergent according to claim 1 , which exhibits an alkaline earth metal content, according to ASTM D4951, of at least 7.0% by mass.

6. An overbased calcium salicylate detergent according to claim 1 , which exhibits a mass ratio of alkaline earth metal to boron is from 1.5 to 5.5.

7. An overbased calcium salicylate detergent according to claim 1 , wherein:
the basicity index is from 5.0 to 8.3;
the ratio of soap content to mass % boron is between 70 and 275 mmol/kg;
the TBN, measured according to ASTM D2896, is from 265 to 350 mg KOH/g;
the combined calcium and magnesium content, according to ASTM D4951, is from 7.0% to 12.5% by mass;
the boron content, according to ASTM D4951, is from 3.5% to 6.8% by mass;
the soap content is from 350 to 500 mmol/kg;
the mass ratio of alkaline earth metal to boron is from 1.7 to 4.5;
the mass ratio of borate to carbonate moieties is from 1.6 to 3.0; and
the hydrocarbyl substitution comprises a C 14 to C 19 alkyl or alkenyl moiety.

8. A method for making a package-stable overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent comprising both carbonate and borate moieties, the method comprising the steps of:
providing an oil-soluble or oil-dispersible overbased but unborated alkaline earth metal hydrocarbyl-substituted salicylate detergent made by reacting a mineral oil solution of an acid with a stoichiometric excess of a neutralizing agent comprising an alkaline earth metal carbonate or bicarbonate, optionally in the presence of promoter, at a temperature from 60 to 200° C. for a sufficient period of time to have thereby formed the overbased but unborated alkaline earth metal hydrocarbyl-substituted salicylate detergent, which exhibits a basicity index of at least 3.5, a soap content of at least 330 mmol/kg and less than or equal to 500 mmol/kg, an alkaline earth metal content, measured according to ASTM D4951, of at least 7.0% by mass, and a TBN, according to ASTM D2896, of at least 240 mg KOH/g, wherein the alkaline earth metal comprises calcium and/or magnesium, wherein the overbased but unborated alkaline earth metal hydrocarbyl-substituted salicylate detergent comprises carbonate moieties, and wherein the hydrocarbyl substitution comprises 9 to 30 carbon atoms;
admixing said overbased but unborated alkaline earth metal hydrocarbyl-substituted salicylate detergent in an organic diluent medium comprising an aprotic hydrocarbon solvent and a C 1 -C 4 primary alcohol but comprising no intentionally added water with a boron source at a temperature below 100° C. to form a reaction mixture;
heating the reaction mixture to a temperature from 105° C. to 225° C. at a heating rate below 3° C./min in a borating process to form a crude borated detergent product;
optionally, further adding additional aprotic hydrocarbon solvent, thereby still forming a crude borated detergent product; and
removing a significant portion of the diluent medium, as well as water, formed during the borating process, in order to form the overbased alkaline earth metal hydrocarbyl-substituted salicylate detergent according to claim 1 .

9. The method according to claim 8 , wherein:
the aprotic hydrocarbon solvent comprises benzene, xylene, toluene, mesitylene, naphthalene, cyclohexane, cyclooctane, heptane, octane, decane, dodecane, or a combination thereof; and
the boron source comprises orthoboric acid, metaboric acid, tetraboric acid, monoammonium borate, diammonium borate, triammonium borate, C 1 -C 4 alkyl dihydrogen borate, di-C 1 -C 4 alkyl hydrogen borate, tri-C 1 -C 4 alkyl borate, or a combination thereof.

10. A lubricant additive package concentrate comprising:
less than 40% by mass of a Group I, Group II, and/or Group III lubricating oil basestock;
at least 0.5% by mass of the boron-containing overbased calcium salicylate detergent according to claim 1 ;
at least one ashless dispersant;
at least one antioxidant;
at least one friction modifier; and
optionally, one or more of an additional detergent, a corrosion inhibitor, an antiwear agent, a seal swelling agent, an anti-foamant, an extreme pressure agent, a viscosity modifier, and a pour point depressant.

11. A lubricant additive package concentrate according to claim 10 , wherein the at least one friction modifier comprises a substantially sulfur-free ashless organic friction modifier.

12. A lubricant additive package concentrate according to claim 10 , wherein the at least one friction modifier comprises a substantially nitrogen-free and substantially sulfur-free ashless organic friction modifier.

13. A lubricant additive package concentrate according to claim 10 , which exhibits package stability at −60° C. for at least 12 weeks.

14. A lubricating oil composition comprising:
at least 70% by mass of a lubricating oil basestock comprising one or more of Group I, Group II, Group III, and/or Group IV basestocks; and
at least 5% by mass of the lubricant additive package concentrate according to claim 10 .

15. A lubricating oil composition comprising:
at least 85% by mass of a lubricating oil basestock comprising one or more of Group I, Group II, Group III, and/or Group IV basestocks;
at least 0.05% by mass of the boron-containing overbased calcium salicylate detergent according to claim 1 ;
at least one ashless dispersant;
at least one antioxidant;
at least one friction modifier; and
optionally, one or more of an additional detergent, a corrosion inhibitor, an antiwear agent, a seal swelling agent, a tackifier, a demulsifier, an anti-foamant, an extreme pressure agent, a viscosity modifier, and a pour point depressant.

16. A lubricating oil composition comprising:
at least 85% by mass of a lubricating oil basestock comprising one or more of Group I, Group II, Group III, and/or Group IV basestocks;
at least 0.05% by mass of the boron-containing overbased calcium salicylate detergent made according to the method of claim 8 ;
at least one ashless dispersant;
at least one antioxidant;
at least one friction modifier; and
optionally, one or more of an additional detergent, a corrosion inhibitor, an antiwear agent, a seal swelling agent, a tackifier, a demulsifier, an anti-foamant, an extreme pressure agent, a viscosity modifier, and a pour

Assignees

• Infineum Int Ltd

Inventors

• Wilkinson Thomas Daniel
• Delamore Oliver
• Coxon Alexander
• Popowicz Marcus
• Samonte Ara
• Rana Mallika

Classifications

• C10M139/00 Primary

  Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 · CPC title

• C07C65/10

  Salicylic acid · CPC title

• C10M169/04

  Mixtures of base-materials and additives · CPC title

• C10M2203/003

  used as base material · CPC title

• C10M2227/061

  Esters derived from boron · CPC title