METHYLENE BETA-DIKETONE MONOMERS, METHODS FOR MAKING METHYLENE BETA-DIKETONE MONOMERS, POLYMERIZABLE COMPOSITIONS AND PRODUCTS FORMED THEREFROM
The present teachings are directed at polymers, polymeric compositions, polymerizable compositions, and articles including a 1,1-disubstituted alkene monomers (e.g., methylene beta-diketone monomers) and one or more formulation materials. The monomer preferably is a high purity monomer. Preferably, the amount of ketals (e.g., in the polymerizable composition) is less than about 100 ppm and/or the amount of latent acid-forming impurities (e.g., in the polymerizable composition) is less than about 100 ppm (e.g., based on the total weight of the monomer). Preferably, the methylene beta-diketone monomer is a high purity monomer having a purity of about 95 weight percent or more. The monomer(s) may be employed in compositions and products, 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 polymerizable composition comprising:
i) at least one methylene beta-diketone monomer; and
ii) one or more formulation materials selected including an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a toughening agent, a plasticizing agent, a thixotropic agent, a cross-linking agent, a reinforcing agent, a dye, a filler, an opacifier, a thermal degradation reducer, a natural or synthetic rubber, an adhesion promotor, or any combination thereof;
wherein the methylene beta-diketone has the structural formula:
wherein R 1 and R 2 are independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl-(C 1 -C 15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy —(C 1 -C 15 alkyl), each of which may be optionally substituted by C 1 -C 15 alkyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl —(C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
or
wherein R 1 and R 2 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C 1 -C 15 alkyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl —(C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
wherein the amount of ketals in the polymerizable composition is less than about 100 ppm and/or the amount of latent acid-forming impurities in the polymerizable composition is less than about 100 ppm.
2 . The polymerizable composition of claim 1 , wherein the formulation material includes the thixotropic agent.
3 . The polymerizable composition of claim 1 , wherein the formulation material includes the toughening agent.
4 . The polymerizable composition of claim 1 , wherein the formulation material includes a natural or synthetic rubber.
5 . The polymerizable composition of claim 1 , wherein the formulation material includes an acrylic rubber or an ethylene/acrylic elastomer.
6 . The polymerizable composition of claim 1 , wherein the formulation material includes a cross-linking agent, a cure accelerator, or both.
7 . The polymerizable composition of claim 1 , wherein the formulation material includes an adhesion promotor.
8 . The polymerizable composition of claim 1 , wherein the formulation material includes a thixotropic agent.
9 . The polymerizable composition of claim 1 , wherein the formulation material includes a reinforcing agent, a dye, a filler, or an opacifier.
10 . A polymer prepared from the polymerizable composition of claim 1 , wherein the polymer includes repeat units formed from the methylene beta-diketone monomer.
11 . A polymerizable composition comprising:
i) at least one methylene beta-diketone monomer; and
ii) one or more formulation materials selected including an acidic stabilizer, a free radical stabilizer, a sequestering agent, a cure accelerator, a rheology modifier, a toughening agent, a plasticizing agent, a thixotropic agent, a cross-linking agent, a reinforcing agent, a dye, a filler, an opacifier, a thermal degradation reducer, a natural or synthetic rubber, an adhesion promotor, or any combination thereof;
wherein the methylene beta-diketone has the structural formula:
wherein R 1 and R 2 are independently C 1 -C 15 alkyl, C 2 -C 15 alkenyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl-(C 1 -C 15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy —(C 1 -C 15 alkyl), each of which may be optionally substituted by C 1 -C 15 alkyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl —(C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
or
wherein R 1 and R 2 are taken together with the atoms to which they are bound to form a 5-7 membered heterocyclic ring which may be optionally substituted by C 1 -C 15 alkyl, halo-(C 1 -C 15 alkyl), C 3 -C 6 cycloalkyl, halo-(C 3 -C 6 cycloalkyl), heterocyclyl, heterocyclyl-(C 1 -C 15 alkyl), aryl, aryl —(C 1 -C 15 alkyl), heteroaryl, C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
wherein the methylene beta-diketone monomer is a high purity monomer having a purity of about 95 weight percent or more.
12 . The polymerizable composition of claim 11 , wherein the formulation material includes the thixotropic agent.
13 . The polymerizable composition of claim 11 , wherein the formulation material includes the toughening agent.
14 . The polymerizable composition of claim 11 , wherein the formulation material includes a natural or synthetic rubber.
15 . The polymerizable composition of claim 11 , wherein the formulation material includes an acrylic rubber or an ethylene/acrylic elastomer.
16 . The polymerizable composition of claim 11 , wherein the formulation material includes a cross-linking agent, a cure accelerator, or both.
17 . The polymerizable composition of claim 11 , wherein the formulation material includes an adhesion promotor.
18 . The polymerizable composition of claim 11 , wherein the formulation material includes a thixotropic agent.
19 . The polymerizable composition of claim 11 , wherein the formulation material includes a reinforcing agent, a dye, a filler, or an opacifier.
20 . A polymer prepared from the polymerizable composition of claim 11 , wherein the polymer includes repeat units formed from the methylene beta-diketone monomer.