Metal compounds of calixarenes, detergent compositions containing them and use thereof in lubricant compositions

Patent metadata

Field	Value
Publication number	US-10807939-B2
Application number	US-201615751506-A
Country	US
Kind code	B2
Filing date	Aug 10, 2016
Priority date	Aug 10, 2015
Publication date	Oct 20, 2020
Grant date	Oct 20, 2020

Abstract

The present invention relates to a metal compound of calixarene not containing sulfur and dispersible in oil, which can be partially salified, or neutral, or basic or overbased, said calixarene having general formula (I) in which: a) R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, or a group containing carbon and hydrogen, or a group containing in addition to carbon and hydrogen also heteroatoms, provided that said heteroatoms are not sulfur; b) one of the two substituents R 5 and R 6 is hydrogen, while the other may be selected from hydrogen, or a linear or branched alkyl with a number of carbon atoms between 1 and 6, preferably methyl, ethyl, 1-propyl, 2-propyl, n-butyl, sec-butyl, more preferably methyl or ethyl; c) n is the number of units of the calixarene ring and is comprised in the range between 4 and 16, preferably between 5 and 12; said calixarene being characterized in that in at least one of the n units of the calixarene ring, at least one of the substituents R 1 , R 2 , R 3 and R 4 contains at least one acid group of carboxylic type available for the reaction with a metal base, with the proviso that said acid group of carboxylic type is not contained in a unit of the calixarene ring derived from salicylic acid.

First claim

The invention claimed is:

1. A metal compound of calixarene not containing sulfur and dispersible in oil, which can be partially salified, or neutral, or basic or overbased, said calixarene having general formula (I)

in which:
a) R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen, or a group containing carbon and hydrogen, or a group containing in addition to carbon and hydrogen also a heteroatom, provided that said heteroatom is not sulfur;
b) one of the two substituents R 5 and R 6 is hydrogen, while the other may be selected from hydrogen, or a linear or branched alkyl with a number of carbon atoms between 1 and 6;
c) n is the number of units of the calixarene ring and is comprised in the range between 4 and 16;
wherein in at least one of the n units of the calixarene ring, at least one of the substituents R 1 , R 2 , R 3 and R 4 contains at least one acid group of carboxylic type available for reaction with a metal base, with the proviso that said acid group of carboxylic type is not contained in a unit of the calixarene ring derived from salicylic acid.

2. The metal compound according to claim 1 wherein the calixarene having general formula (I) comprises at least two units of the n units of the calixarene ring in which at least one of the substituents R 1 , R 2 , R 3 and R 4 contains at least one acid group of the carboxylic type, with the proviso that said acid group of carboxylic type is not part of a unit of the calixarene ring derived from salicylic acid.

3. The metal compound according to claim 1 wherein the calixarene having general formula (I) comprises a number of units of the ring, between 2 and n, in which one of the substituents R 1 and R 2 contains an acid group of carboxylic type, with the proviso that said acid group of carboxylic type is not part of a unit of the calixarene ring derived from salicylic acid.

4. The metal compound according to claim 1 wherein R 1 is selected from hydrogen; or a linear or branched alkyl having a number of carbon atoms comprised between 1 and 40; or a group containing in addition to carbon and hydrogen also a heteroatom and having a number of carbon atoms comprised between 2 and 24 thereof, provided that said heteroatom is not sulfur, and wherein said group contains one or more acid groups of carboxylic type available for the reaction with a metal base.

5. The metal compound according to claim 1 wherein R 2 is selected from a linear or branched alkyl having a number of carbon atoms between 1 and 40; or a group containing in addition to carbon and hydrogen also a heteroatom and having a number of carbon atoms between 1 and 24, provided that said heteroatom is not sulfur, and wherein said group contains one or more acid groups of carboxylic type available for the reaction with a metal base.

6. The metal compound according to claim 1 wherein R 3 , R 4 , R 5 and R 6 are simultaneously hydrogen.

7. The metal compound according to claim 1 wherein the metal of the metal compound is selected from an alkali metal, an alkaline earth metal, and any other metal whose basic compound is capable of forming a salt with a calixarene.

8. The metal compound according to claim 7 wherein the metal is selected from calcium and magnesium.

9. The metal compound according to claim 7 wherein the metal content corresponds to a ratio between the metal equivalents and acid ones of the calixarene from which it is derived comprised between 0.2 and 15.

10. A detergent composition comprising the metal compound of calixarene according to claim 1 .

11. The detergent composition according to claim 10 wherein the metal compound of calixarene is present at a concentration, expressed as the weight percentage of said metal compound of calixarene of formula (I) with respect to the detergent composition, comprised between 5% and 100%.

12. The detergent composition according to claim 10 which further comprises at least one metal compound of an organic acid compound selected from:
A. a metal compound, partially salified, neutral, basic or overbased of an oligomeric compound of formula (IV)

 or of a monomeric compound of formula (V)

in which:
R 9 , R 10 , R 12 , R 13 , R 16 , R 17 , R 18 , R 19 , R 22 , R 23 , R 24 and R 25 are independently selected from hydrogen, a group containing carbon and hydrogen, a group containing in addition to carbon and hydrogen also a heteroatom, provided that sulfur is not present;
R 14 , R 15 , R 20 and R 21 are selected from hydrogen or an alkyl with a number of carbon atoms between 1 and 6;
R 11 and R 26 are independently selected from hydrogen, the hydroxymethylene group —CH 2 OH, methyl and the hydroxycarbonyl group —COOH;
P is a number in the range between 0 and 20; or

B. a metal compound, partially salified, neutral, basic or overbased of a carboxylic, dicarboxylic and polycarboxylic acid containing a number of carbon atoms between 6 and 80, comprising an alkyl-carboxylic acid of formula (VI):

in which:
R 27 is selected from a linear or branched alkyl or alkenyl group, containing a number of carbon atoms between 6 and 40;
R 28 is selected from hydrogen, an alkyl group containing from 1 to 4 carbon atoms, or —CH 2 COOH; or

C. a metal compound, partially salified, neutral, basic or overbased of a compound of formula (VII):

in which R 29 , R 30 , R 31 , R 32 , R 33 , and R 34 are independently selected from hydrogen, a group containing carbon and hydrogen, a group containing in addition to carbon and hydrogen also a heteroatom, provided that sulfur is not present; or

D. a metal compound, partially salified, neutral, basic or overbased of a phenol substituted with a linear or branched alkyl group, in number comprised between 1 and 3, each containing a number of carbon atoms comprised between 2 and 40; or
E. a metal compound, partially salified, neutral, basic or overbased of a salicylic acid substituted with a linear or branched alkyl group in number comprised between 1 and 3, each containing a number of carbon atoms comprised between 2 and 40; or
F. a metal compound, partially salified, basic or overbased of calixarene of the general formula (Z) having substituents of hydroxyl type:

in which Y is a divalent bridge group; R 3 is a group containing carbon and hydrogen, or a group containing in addition to carbon and hydrogen also a heteroatom; n is an integer between 3 and 9, and alternatively:
R 1 is hydroxyl and R 2 and R 4 are independently hydrogen, or a group containing carbon and hydrogen, or a group containing in addition to carbon and hydrogen also a heteroatom; or
R 2 and R 4 are hydroxyl groups and R 1 is independently hydrogen, or a group containing carbon and hydrogen, or a group containing in addition to carbon and hydrogen also a heteroatom.

13. The

Assignees

• Eni Spa

Inventors

• Notari Marcello
• Roselli Alberto
• Casnati Alessandro
• Sansone Francesco
• Burlini Alessandro

Classifications

• C10M175/0033

  using distillation processes; devices therefor · CPC title

• C10M177/00

  Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes · CPC title

• C10M107/28

  containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate · CPC title

• C10M2207/262

  derived from hydroxy substituted aromatic acids, e.g. salicylates · CPC title

• C11D3/187

  aromatic · CPC title