Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
The present invention provides methylene beta-diketone monomers, methods for producing the same, and compositions and products formed therefrom. In the method for producing the methylene beta-diketones of the invention, a beta-diketone is reacted with a source of formaldehyde in a modified Knoevenagel reaction optionally in the presence of an acidic or basic catalyst, and optionally in the presence of an acidic or non-acidic solvent, to form reaction complex. The reaction complex may be an oligomeric complex. The reaction complex is subjected to further processing, which may be vaporization by contact with an energy transfer means in order to isolate the beta-diketone monomer. The present invention further compositions and products formed from methylene beta-diketone monomers of the invention, including monomer-based products (e.g., inks, adhesives, coatings, sealants or reactive molding) and polymer-based products (e.g., fibers, films, sheets, medical polymers, composite polymers and surfactants).
1. A methylene beta-diketone monomer having a structural formula selected from the group consisting of:
2. The monomer of claim 1 , wherein the methylene beta-diketone monomer has the structural formula:
3. The monomer of claim 1 , wherein the monomer has the structural formula selected from the group consisting of:
4. The monomer of claim 1 , wherein the monomer has the structural formula selected from the group consisting of:
5. The monomer of claim 1 , wherein the monomer has the structural formula
6. A polymerizable composition including at least one methylene beta-diketone monomer according to claim 1 .
7. The polymerizable composition according to claim 6 further comprising a stabilizing amount of at least one stabilizer selected from the group consisting of: an acidic stabilizer, a vapor phase stabilizer, and a free radical stabilizer.
8. The polymerizable composition according to claim 7 wherein the at least one stabilizer includes the acidic stabilizer selected from trifluoromethane sulfonic acid, maleic acid, methane sulfonic acid, difluoro acetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid, and chlorodifluoro acid.
9. The polymerizable composition according to claim 7 wherein the at least one stabilizer includes the vapor phase stabilizer selected from hydroquinone, methyl hydroquinone, butylated hydroxytoluene, butylated hydroxyanisole.
10. The methylene beta-diketone monomer according to claim 1 being formed as a reaction product of a 1,3-disubstituted-propane-1,3-dione represented by a structural formula selected from the group consisting of:
and a source of formaldehyde.
11. A method of preparing a methylene beta-diketone monomer comprising:
a) reacting a beta-diketone reactant having the structural formula selected from the group consisting of:
with a source of formaldehyde, optionally in the presence of an acidic or basic catalyst, and optionally in the presence of an acidic or non-acidic solvent, to form a reaction complex; and
b) isolating a methylene beta-diketone monomer from the reaction complex, wherein the methylene beta-diketone monomer has the structural formula selected from the group consisting of:
12. The method according to claim 11 wherein in step (b), isolating the methylene beta-diketone monomer comprises:
i. contacting the reaction complex, or a portion thereof, with an energy transfer means to produce a vapor phase including the methylene beta-diketone monomer; and
ii. collecting the methylene beta-diketone monomer from the vapor phase.
13. The method of claim 11 , wherein in step (b), isolating the methylene beta-diketone monomer comprises:
i. heating the reaction complex, or a portion thereof, to a temperature between about 130° C. and about 300° C. to produce a vapor phase including the methylene beta-diketone monomer; and
ii. collecting the methylene beta-diketone monomer from the vapor phase.
14. The method according to claim 11 wherein the reaction conditions include:
a) an initiating temperature of between about 60° C. and about 130° C.; and
b) atmospheric pressure.
15. A polymer having repeat units of the formula selected from the group consisting of:
and combinations thereof.
16. An oligomeric complex prepared by reacting a beta-diketone reactant with a source of formaldehyde; optionally in the presence of heat transfer agent; optionally in the presence of an acidic or basic catalyst; and optionally in the presence of an acidic or non-acidic solvent, the oligomeric complex having between 2 and 12 repeat units having the structural formula selected from the group consisting of:
and combinations thereof.