Cycloalkyl phenylenediamines as deposit control agents for lubricants

A method for stabilizing an organic material subject to oxidative, thermal, or light-induced degradation comprising adding to the organic material a stabilizing amount of at least one N-cycloalkyl-substituted phenylenediamine additive of the structure:

• wherein
• X is
• Y is
• R1 is a cycloalkyl ring selected from the group consisting of:
• wherein
• R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, allyl, methyallyl, isobutenyl, alkenyl, furfuryl, benzyl, alkaryl, and phenyl;
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• m is an integer of 1 to 8;
• and
• wherein, when X and Y are para to each other, R2, R3, and R4 are in an interrelated relationship selected from the group consisting of:
• (A) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• R3 is an independently selected cycloalkyl ring of the structure:
• wherein Q and m are as defined above;
• and
• R4 is selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl, and alkenyl of from 3 to about 36 carbon aims, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that Z is not—CH2CH2— or —CH2CH(CH3)—;
• (B) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and
• wherein Q and m are as defined above;
• and
• R3 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl and alkenyl of from 3 to about 36 carbon atoms, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, that Z is not —CH2CH2— or —CH2CH(CH3)—, and that R3 and R4 are not both hydrogen;
• (C) R3 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• R2 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl, and alkenyl of from 3 to about 36 carbon atoms, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, and that Z is not —CH2CH2— or —CH2CH(CH3)—;
• (D) R2, R3, and R4 are independently selected from the group consisting of alkyls of from 3 to about 36 carbon atoms, alkenyls of from 3 to about 36 carbon atoms, aryl, alkaryl, and cycloalkyl, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, that Z is not —CH2CH2— or —CH2CH(CH3)—;
• and
• (1) at least two of R2, R3, and R4 are independently selected from the group consisting of alkyls of from 3 to about 36 carbon atoms, alkenyls of from 3 to about 36 carbon atoms, wherein said alkyls or alkenyls are branched on the carbon bonded to the phenylenediamine nitrogen;
• and that
• (2) when R1 is a 2,2,6,6-tetramethylpiperidinyl, R3 can be hydrogen;
• and
• wherein, when X and Y are ortho or meta to each other, R2, R3, and R4 are in an interrelated relationship selected from the group consisting of:
• (E) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• R3 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, and cycloalkyl, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, alkenyl of from 3 to about 36 carbon atoms, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that Z is not—CH2CH2— or —CH2CH(CH3)—, and that R3 and R4 are not both hydrogen;
• (F) R2, R3, and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms and cycloalkyl, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, aryl, alkaryl, alkenyl of from 3 to about 36 carbon atoms, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;provided that Z is not —CH2CH2— or —CH2CH(CH3)—;
• and wherein said phenylenediamine is in the form of a free base, or an oil-soluble salt.

A compound comprising the structure:

• R1 is a cycloalkyl ring selected from the group consisting of:
• wherein
• R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, allyl, methyallyl, isobutenyl, alkenyl, furfuryl, benzyl, alkaryl, and phenyl;
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• m is an integer of 1 to 8;
• and
• wherein, when X and Y are para to each other, R2, R3, and R4 are in an interrelated relationship selected from the group consisting of:
• (A) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• R3 is an independently selected cycloalkyl ring of the structure:
• wherein Q and m are as defined above;
• and
• R4 is selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl, and alkenyl of from 3 to about 36 carbon atoms, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that Z is not —CH2CH2— or —CH2CH(CH3)—;
• (B) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and
• wherein Q and m are as defined above;
• and
• R3 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl, and alkenyl of from 3 to about 36 carbon atoms, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, that Z is not —CH2CH2— or —CH2CH(CH3)—, and that R3 and R4 are not both hydrogen;
• (C) R3 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• R2 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, cycloalkyl, and alkenyl of from 3 to about 36 carbon atoms, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, and that Z is not —CH2CH2— or —CH2CH(CH3)—;
• (D) R2, R3, and R4 are independently selected from the group consisting of alkyls of from 3 to about 36 carbon atoms, alkenyls of from 3 to about 36 carbon atoms, aryl, alkaryl, and cycloalkyl, all optionally containing a nitrogen atom, hydrogen, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that R3 and R4 are not 2-hydroxyethyl, that Z is not —CH2CH2— or —CH2CH(CH3)—;
• and
• (1) at least two of R2, R3, and R4 are independently selected from the group consisting of alkyls of from 3 to about 36 carbon atoms, alkenyls of from 3 to about 36 carbon atoms, wherein said alkyls or alkenyls are branched on the carbon bonded to the phenylenediamine nitrogen;
• and that
• (2) when R1 is a 2,2,6,6-tetramethylpiperidinyl, R3 can be hydrogen;
• and
• wherein, when X and Y are ortho or meta to each other, R2, R3, and R4 are in an interrelated relationship selected from the group consisting of:
• (E) R2 is a cycloalkyl ring independently selected from the group consisting of:
• wherein
• each Q is C(R9)(R10), wherein each R9 and R10 is independently selected from the group consisting of hydrogen, linear and branched alkyl groups of from 1 to 20 carbon atoms, and cycloalkyl;
• wherein R11 is H, linear and branched alkyl groups of from 1 to 20 carbon atoms, cycloalkyl, aryl, alkaryl, and O;
• and wherein Q and m are as defined above;
• and
• R3 and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms, aryl, alkaryl, and cycloalkyl, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, alkenyl of from 3 to about 36 carbon atoms, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;
• provided that Z is not—CH2CH2— or —CH2CH(CH3)—, and that R3 and R4 are not both hydrogen;
• (F) R2, R3, and R4 are independently selected from the group consisting of linear or branched alkyl of from 1 to about 36 carbon atoms and cycloalkyl, all optionally containing a nitrogen, oxygen, or sulfur atom, hydrogen, aryl, alkaryl, alkenyl of from 3 to about 36 carbon atoms, and ZCO2R11, wherein Z is an alkylene or alkenyl group of from 1 to about 36 carbons, and R11 is selected from the group consisting of linear or branched alkyl, cycloalkyl, aryl, and alkaryl, all optionally containing O, N, or S;provided that Z is not —CH2CH2— or —CH2CH(CH3)—;
• and wherein said phenylenediamine is in the form of a free base, or an oil-soluble salt.

A compound selected from the group consisting of:

• N-(1-methyldecyl)-N′-(2,2,6,6-tetramethyl-4-piperdinyl)-p-phenylenediamine;
• N-cyclohexyl-N-phenyl-o-phenylenediamine;
• N,N′-dicyclohexyl-m-phenylenediamine;
• N,N′-dicyclohexyl-m-toluenediamine;
• N,N′-dicyclohexyl-3,5-diethyl-2,4-toluenediamine;
• N,N′-dicyclohexyl-3,5-diethyl-2,6-toluenediamine;
• N-cyclohexyl-N-(2-ethylhexyl)N′-phenyl-p-phenylenediamine;
• N-cyclohexyl-N,N′-di(sec-butyl)-p-phenylenediamine;
• N,N′-dicyclooctyl-N-ethyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N-isopropyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N-isobutyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N-butyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N-butyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N-isobutyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N-isobutyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N-heptyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N-heptyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N-phenyl-p-phenylenediamine;
• N,N-dicyclohexyl-N′-phenyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-difurfuryl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-dibenzyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N′-phenyl-N-heptyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-diethyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-dibutyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-dibutyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-diisobutyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-diisobutyl-p-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-diheptyl-m-phenylenediamine;
• N,N′-dicyclohexyl-N,N′-diheptyl-p-phenylenediamine;
• N,N′-dicyclooctyl-N,N′-diethyl-p-phenylenediamine;
• N,N,N′-tricyclopentyl-p-phenylenediamine;
• N,N,N′-tricyclohexyl-p-phenylenediamine;
• N,N,N′-tricyclohexyl-N′-heptyl-p-phenylenediamine;
• N,N,N′-tricyclohexyl-N′-propyl-p-phenylenediamine;
• N,N,N′-tricyclohexyl-N′-butyl-p-phenylenediamine;
• N-(2-ethylhexyl)-N,N′,N′-tricyclohexyl-p-phenylenediamine;
• N,N,N′-tricyclohexyl-N′-phenyl-p-phenylenediamine;
• N,N,N′,N′-tetracyclohexyl-p-phenylenediamine;
• N,N′-bis(2-decalinyl)-p-phenylenediamine;
• N,N′-dicyclohexyl-4,6-diisobutyl-1,3-phenylenediamine;
• and
• N,N′-dicyclohexyl-4-isobutenyl-6-isobutyl-1,3-phenylenediamine.