Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom

Patent metadata

Field	Value
Publication number	US-9828324-B2
Application number	US-201514868795-A
Country	US
Kind code	B2
Filing date	Sep 29, 2015
Priority date	Oct 20, 2010
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

The present teachings are directed at 1,1-disubstituted alkene monomers (e.g., methylene beta-diketone monomers), methods for producing the same, and compositions and products formed therefrom. In the method for producing the monomer, a beta-diketone is preferably 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 vaporization in order to isolate the monomer. 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).

First claim

What is claimed is:

1. A polymerizable composition comprising:
at least one methylene beta-diketone monomer having 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-(C1-C15 alkyl), heteroaryl or heteroaryl-(C 1 -C 15 alkyl), or alkoxy-(C1-15 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 amount of ketals in the polymerizable composition is less than about 10 ppm and the amount of latent acid-forming impurities in the polymerizable composition is less than about 10 ppm.

3. The polymerizable composition of claim 1 , including 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.

4. The polymerizable composition of claim 3 , wherein the polymerizable composition is an adhesive, a coating, or a sealant.

5. The polymerizable composition of claim 3 , 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.

6. The polymerizable composition of claim 3 , wherein the at least one stabilizer includes the vapor phase stabilizer selected from hydroquinone, methyl hydroquinone, butylated hydroxytoluene, butylated hydroxyanisole.

7. The polymerizable composition of claim 1 , wherein the methylene beta-diketone monomer is formed as a reaction product of a 1,3-disubstituted-propane-1,3-dione represented by R 1 —C(O)—C—C(O)—R 2 , and a source of formaldehyde.

8. The polymerizable composition of claim 7 , wherein the 1,3-disubstituted-propane-1,3-dione is selected from the group consisting of 1,3-dimethyl-propane-1,3-dione; 1,3-diethyl-propane-1,3-dione; 1-ethyl-3-methyl-propane-1,3-dione; 1,3-dipropyl-propane-1,3-dione, 1,3-dibutyl-propane-1,3-dione; and 1,3-diphenyl-propane-1,3-dione.

9. A polymerizable composition comprising:
at least one methylene beta-diketone monomer having 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 1-15 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;
wherein the amount of any analogous compound having the methylene group of the methylene beta-diketone replaced by a hydroxyalkyl group is about 3 mole percent or less, based on the total moles of the methylene beta-diketone monomer.

10. The polymerizable composition of claim 9 , wherein any impurities in the monomer, if present, includes about 40 mole percent or more of the impurity is an analogous 1,1-disubstituted alkane compound.

11. The polymerizable composition of claim 9 , wherein the concentration of any impurities having a dioxane group is about 2 mole percent or less, based on the total weight of the methylene beta-diketone.

12. The polymerizable composition of claim 9 , wherein the polymerizable composition includes 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.

13. The polymerizable composition of claim 9 , wherein the polymerizable composition is an adhesive, a coating, or a sealant.

14. The polymerizable composition of claim 9 , wherein the methylene beta-diketone monomer is formed as a reaction product of a 1,3-disubstituted-propane-1,3-dione represented by R 1 —C(O)—C—C(O)—R 2 , and a source of formaldehyde.

15. The polymerizable composition of claim 14 , wherein the 1,3-disubstituted-propane-1,3-dione is selected from the group consisting of 1,3-dimethyl-propane-1,3-diones; 1,3-diethyl-propane-1,3-diones; 1-ethyl-3-methyl-propane-1,3-diones; 1,3-dipropyl-propane-1,3-diones, 1,3-dibutyl-propane-1,3-diones; and 1,3-diphenyl-propane-1,3-diones.

16. The polymerizable composition of claim 9 , wherein the methylene beta-diketone monomer has a structural formula selected from the group consisting of:

17. A polymer prepared from the polymerizable composition of claim 9 .

18. A method of preparing the polymerizable composition of claim 9 comprising a step of:
forming a methylene beta-diketone monomer by reacting a 1,3-disubstituted-propane-1,3-dione represented by R 1 —C(O)—C—C(O)—R 2 , and a source of formaldehyde;
wherein the reaction product has a purity of about 97 percent or more.

19. A polymerizable composition comprising:
at least one methylene beta-diketone monomer having 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 1-15 alkyl), each of which may be optionally substituted by C

Assignees

• Sirrus Inc

Inventors

• Sullivan Jeffrey M
• Malofsky Adam G
• Malofsky Bernard M
• Dey Tanmoy

Classifications

• C07C49/84 Primary

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title

• C07C49/557

  having unsaturation outside the rings · CPC title

• C07C49/796

  polycyclic · CPC title

• C07C49/794

  having unsaturation outside an aromatic ring · CPC title

• C07C49/80

  containing halogen · CPC title