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

Patent metadata

Field	Value
Publication number	US-2017342011-A1
Application number	US-201715678533-A
Country	US
Kind code	A1
Filing date	Aug 16, 2017
Priority date	Oct 20, 2010
Publication date	Nov 30, 2017
Grant date	—

Abstract

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).

First claim

What is claimed is:

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.

Assignees

• Sirrus Inc

Inventors

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

Classifications

• C07C49/80

  containing halogen · CPC title

• C07C49/794

  having unsaturation outside an aromatic ring · CPC title

• 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

• C07C45/75

  Reactions with formaldehyde · CPC title

• C07C49/557

  having unsaturation outside the rings · CPC title