Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon HOE 85/F O36J

Claim 2

A cured reaction product obtained via the Michael reaction in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABCO), fluorides of quaternary ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, tertiary phosphanes of the formula P(CH 2 --Y) 3 in which the Ys are identical or different and denote the radical --OH, --CH 2 CN or --N(Z) 2 in which Z is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the formula P(R 4 ,R 5 ,R 6 ) in which the radicals R 4 , R 5 and R 6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 4 , R 5 and R 6 are identical or different, but at least one of the radicals represents a phenyl radical, and aminophosphoranes of formula (R 7 ,R 8 ,R 9 )P═N--C(R 10 ,R 11 ,R 12 ) in which R 7 , R 8 and R 9 are identical or different and denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 10 , R 11 and R 12 are identical or different and each represents an alkyl radical having 1 to 5 carbon atoms or a phenyl radical of (A) compounds containing at least two R 1 R 2 C═CR 3 --X groups (I) with (B) compounds which contain (a) malonic acid moieties attached by an ester linkage (b) at least two groups containing active H atoms of the type --CH or --SH (II) or (c) at least one active H atom and at least one group of the type (II), in which, in formula (I), X denotes --CO-- which is attached to a further R 1 R 2 C═CR 3 group either directly or via the radical of a polyhydric alcohol or of an amine, R 1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R 2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R' 4 of a monohydric alcohol having up to 12 carbon atoms, --CN, --NO 2 or a--CO--NHR 1 or --CO--R 1 group, and R 3 has the same meaning as R 2 and is identical with or different from the latter.

Claim 3

Reaction product as claimed in claim 1, wherein the radical R 1 R 2 C═CR 3 --X (I) in the compound (A) is derived from at least one acid selected from the groups consisting of acrylic acid, methacrylic acid, maleic acid and its anhydride and the compound (B) contains malonic acid moieties attached by an ester linkage.

Claim 4

Reaction product as claimed in claim 1, wherein the radical R 1 R 2 C═CR 3 --X (I) in which X denotes --CO-- and R 3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and containing 2 to 10 carbon atoms.

Claim 5

Reaction product as claimed in claim 1, wherein the groups (I) in the compounds (A) are attached to an oligomer or polymer.

Claim 6

Reaction product as claimed in claim 1, wherein the compound (A) is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, an epoxide resin each containing OH-groups and amine resin.

Claim 7

Reaction product as claimed in claim 1, wherein the group (II) of the compound (B) is derived: (aa) when it denotes ##STR8## from a compound containing the grouping --CO--CHR 1 --CO--, NC--CHR 1 --CO--, NC--CH 2 --CN, ═PO--CHR 1 --CO--, ═CHR 1 --CN, ═PO--CHR 1 --PO═, or --CO--CHR 1 --NO 2 , and (cc) when it denotes --SH, from at least one component selected from the group consisting of thioalcohol acid ester, amide and a mercaptan.

Claim 8

Reaction product as claimed in claim 1, wherein the compound (B) is derived from an at least bifunctional compound selected from the group consisting of polyols, polyamines and polymercaptans.

Claim 9

Reaction product as claimed in claim 1, wherein the product is present on a substrate.

Claim 10

A process for the preparation of reaction products which comprises reacting via michael reaction compound (A) containing at least two R 1 R 2 C═CR 3 --X groups (I) with compound (B) which contains (a) at least two active H atoms or (b) at least two groups containing active H atoms of the type --AH-- (II) or (c) at least one active H atom and at least one group of the type (II), or which form the corresponding amount of this group (II), in which, in formula (I), X denotes --CO-- which is attached to a further R 1 R 2 C═CR 3 group either directly or via the radical of a polyhydric alcohol or of an amine, R 1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R 2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R' 4 of a monohydric alcohol having up to 12 carbon atoms, --CN, --NO 2 or a CO--NHR 1 or CO--R 1 group, and R 3 has the same meaning as R 2 and is identical with or different from the latter, and in formula (II), --AH-- denotes one of the groupings ##STR9## --NH-- and --SH, under the formation of an oligomeric or polymeric reaction product, the reaction being carried out, in the event that --AH-- represents one of the groups ##STR10## or --SH, in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABCO), halides of quaternary ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, organic phosphonium salts having 1 to 20 carbon atoms in the alkyl radical or aryl radical or both, tertiary phosphanes of the general formula P(CH 2 --Y) 3 in which the Ys are identical or different and denote the radical --OH, --CH 2 CN or --N(Z) 2 in which Z is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the general formula P(R 4 ,R 5 ,R 6 ) in which the radicals R 4 , R 5 and R 6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 4 , R 5 and R 6 are identical of different but at least one of the radicals represents a phenyl radical, and aminophosphoranes of the general formula (R 7 ,R 8 ,R 9 )P═N--C(R 10 ,R 11 ,R 12 ) in which R 7 , R 8 and R 9 are identical or different and denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 10 , R 11 and R 12 are identical or different and each represents an alkyl radical having 1 to 5 carbon atoms or a phenyl radical.

Claim 11

A process for the preparation of reaction products which comprises reacting via michael reaction compound (A) containing at least two R 1 R 2 C═CR 3 --X groups (I) with compound (B) which contains (a) at least two active H atoms or (b) at least two groups containing active H atoms of the type --AH-- (II) or (c) at least one active H atom and at least one group of the type (II), or which form the corresponding amount of this group (II), in which, in formula (I), X denotes --CO-- which is attached to a further R 1 R 2 C═CR 3 group either directly or via the radical of a polyhydric alcohol or of an amine, R 1 denotes hydrogen or a hydrocarbon radical having 1 to 10 carbon atoms, R 2 denotes hydrogen, a hydrocarbon radical having 1 to 10 carbon atoms, an ester group containing the radical R' 4 of a monohydric alcohol having up to 12 carbon atoms, --CN, --NO 2 or a CO--NHR 1 or CO--R 1 group, and R 3 has the same meaning as R 2 and is identical with or different from the latter, and in formula (II), --AH-- denotes one of the groupings ##STR9## --NH-- and --SH, under the formation of an oligomeric or polymeric reaction product, the reaction being carried out, in the event that --AH-- represents one of the groups ##STR10## or --SH, in the presence of at least one catalyst selected from the group consisting of diazabicyclooctane (DABCO), halides of quaternary ammonium compounds, on their own or as a mixture with alkyl silicates, amidines, organic phosphonium salts having 1 to 20 carbon atoms in the alkyl radical or aryl radical or both, tertiary phosphanes of the general formula P(CH 2 --Y) 3 in which the Ys are identical or different and denote the radical --OH, --CH 2 CN or --N(Z) 2 in which Z is an alkyl radical having 1 to 5 carbon atoms, tertiary phosphanes of the general formula P(R 4 ,R 5 ,R 6 ) in which the radicals R 4 , R 5 and R 6 denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 4 , R 5 and R 6 are identical of different but at least one of the radicals represents a phenyl radical, and aminophosphoranes of the general formula (R 7 ,R 8 ,R 9 )P═N--C(R 10 ,R 11 ,R 12 ) in which R 7 , R 8 and R 9 are identical or different and denote an alkyl radical having 1 to 12 carbon atoms or a phenyl radical which is unsubstituted or substituted by at least one alkyl, alkoxy or dialkylamino group each of which has 1 to 4 carbon atoms in the alkyl radical, and R 10 , R 11 and R 12 are identical or different and each represents an alkyl radical having 1 to 5 carbon atoms or a phenyl radical.

Claim 12

The process as claimed in claim 9, wherein the catalysts employed are fluorides or phosphanes.

Claim 13

The process as claimed in claim 9, wherein the catalysts employed are trishydroxymethylphosphane, trisdimethylaminomethylphosphane, tris-p-anisylphosphane, methyldiphenylphosphane, methyl di-p-anisylphosphane or α,α-dimethylbenzyliminotributylphosphorane.

Claim 14

A process as claimed in claim 9, werein the reaction is carried out at a temperature from -10° to 180° C.

Claim 15

A process as claimed in claim 9, wherein a component (A) is reacted in which the radical R 1 R 2 C═CR 3 --X (I) in which X denotes --CO-- and R 3 denotes hydrogen or alkyl having 1 to 8 carbon atoms, is derived from a monounsaturated or polyunsaturated carboxylic acid having a basicity of not more than two and containing 2 to 10, preferably 3 to 6, carbon atoms, preferably acrylic acid, methacrylic acid and/or maleic acid.

Claim 16

A process as claimed in claim 9, wherein a compound A is reacted which groups (I) are attached to an oligomer and/or polymer.

Claim 17

A process as claimed in claim 9, wherein a compound (A) is reacted which is derived from at least one resin selected from the group consisting of a polyester, an acrylic resin, epoxide resin each containing OH-groups and amine resin.

Claim 18

A process as claimed in claim 9, wherein a compound (B) is reacted in which the grouping --AH--(II) is derived (aa) when it denotes ##STR11## from a compound containing the grouping --CO--CHR 1 --CO--, NC--CHR 1 --CO--, NC--CH 2 --CN, ═PO--CHR 1 --CO--, ═CHR 1 --CN, ═PO--CHR 1 --PO═, or --CO--CHR 1 --NO 2 , (bb) when it denotes --NH--, from a primary or secondary polyamine or both and (cc) when it denotes --SH, from at least one component selected from the group consisting of thioalcohol acid ester, amide and a mercaptan.

Claim 19

A process as claimed in claim 9, wherein a compound (B) is reacted which is derived from an at least bifunctional compound selected from the group consisting of polyols, polyamines and polymercaptans.