Low temperature Michael addition reactions

A process for the alkylation of .beta.-dicarbonyl compounds having the structure formula:

• ##STR9## wherein R is selected from the group consisting of H, hydrocarbyl moieties, and substituted hydrocarbyl moieties;
• with the proviso that no R-group is sufficiently acidic to neutralize the base catalyst employed for said alkylation;
• and
• X is selected from the group consisting of OR, NR.sub.2, CR.sub.3, aromatic or substituted aromatic moieties having 6 to 10 carbon atoms, and polymeric moieties with
• an .alpha.,.beta.-unsaturated compound having the structural formula:
• ##STR10## wherein R' is H, methyl, CN acetyl, or --CO.sub.2 R;
• wherein R is as defined above;
• R" is selected from the group consisting of H, methyl, methoxy, ethoxy, and --CO.sub.2 R;
• wherein R is as defined above;
• and
• X' is selected from the group consisting of OR, NR.sub.2 and CR.sub.3 ;
• wherein R is as defined above;
• C.sub.1 -C.sub.20 alkyl or substituted alkyl;
• C.sub.6 -C.sub.10 aryl or substituted aryl;
• and a polymeric moiety with the proviso that no group R', R", X or X' is sufficiently acidic to neutralize the base catalyst employed for said alkylation;
• said process comprising contacting said .beta.-dicarbonyl compound and said .alpha.,.beta.-unsaturated compound in the presence of at least one base selected from the group consisting of compounds having the structural formula:
• ##STR11## wherein R.sup.1 .dbd.C.sub.1 -C.sub.20 alkyl, aryl, aralkyl or alkaryl moiety;
• R.sup.2, R.sup.3 and R.sup.4 are each independently selected from H, C.sub.1 -C.sub.20 alkyl or aralkyl, wherein any two or more of R.sup.1,
• R.sup.2, R.sup.3 and R.sup.4 can be interconnected as part of a ring structure;
• and ##STR12## wherein each of R.sup.5 -R.sup.9 are independently selected from H, C.sub.1 -C.sub.20 alkyl or aralkyl, wherein any two or more of R.sup.5 -R.sup.9 can be interconnected as part of a ring structure wherein said contacting results in crosslinking of a thermoset material comprising said .beta.-dicarbonyl compound and said .alpha.,.beta.-unsaturated compound and wherein said thermoset material is first applied to a substrate and subjected to a preliminary curing at a temperature in the range of 10.degree.-40.degree. C., followed by a second curing treatment at a temperature in the range of 40.degree.-120.degree. C.