Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom

Patent metadata

Field	Value
Publication number	US-10604601-B2
Application number	US-201815978974-A
Country	US
Kind code	B2
Filing date	May 14, 2018
Priority date	Oct 19, 2011
Publication date	Mar 31, 2020
Grant date	Mar 31, 2020

Abstract

The present invention provides multifunctional monomers, including, but not limited to include multifunctional methylene malonate and methylene beta-ketoester monomers; methods for producing the same; and compositions and products formed therefrom. The multifunctional monomers of the invention may be produced by transesterification or by direct synthesis from monofunctional methylene malonate monomers or methylene beta-ketoester monomers. The present invention further compositions and products formed from methylene beta-ketoester 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).

First claim

What is claimed is:

1. A multifunctional monomer having the formula:

wherein:
each instance of 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), aryl, aryl-(C1-C15 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), aryl, aryl —(C 1 -C 15 alkyl), C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
[A] is independently selected from a polybutadienyl linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, a polycarbonate linking group, a polyester linking group, a C 3 -C 6 cycloalkyl linking group, a triol linking group, or a dimethyl benzene linking group;
and
each instance of Q is —O— or a direct bond.

2. A multifunctional monomer according to claim 1 ,
wherein [A] is independently selected a polybutadienyl linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, polycarbonate linking group, C 3 -C 6 cycloalkyl linking group or a triol linking group.

3. A multifunctional monomer according to claim 1 ,
wherein:
[A] is independently selected from a linking group derived from any isomer of cyclohexane dimethanol or trimethylol propane.

4. A multifunctional monomer according to claim 1 ,
wherein
each instance of R 1 and R 2 are independently C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl; and
-[A]- is independently selected from a C 3 -C 6 cycloalkyl.

5. The multifunctional monomer according to claim 1 , wherein each instance Q is —O—.

6. The multifunctional monomer according to claim 1 , wherein each instance Q is a direct bond.

7. A multifunctional monomer according to claim 1 , having the formula:

8. A multifunctional monomer according to claim 1 , having the formula:

9. A multifunctional monomer according to claim 1 , having the formula:

10. A multifunctional monomer according to claim 1 , wherein A is independently selected from a polyester linking group and the polyester linking group is selected from copolymers containing styrene, acrylonitrile, ethers, and ketones that contain ester functionality to allow ester interchange.

11. A multifunctional monomer according to claim 1 , wherein R 1 and R 2 are selected from C 1-6 alkyl or a C 3 -C 6 cycloalkyl.

12. A multifunctional monomer having the formula:

wherein:
each instance of 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), aryl, aryl-(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), aryl, aryl —(C 1 -C 15 alkyl), C 1 -C 15 alkoxy, C 1 -C 15 alkylthio, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester;
-[A]- is independently selected from a polybutadienyl linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group, a polyester linking group, polytetrahydrofuran, a C 3 -C 6 cycloalkyl linking group, a triol linking group, or a dimethyl benzene linking group;
m is an integer from 1 to 25; and
each instance of Q is independently selected from —O— or a direct bond.

13. A multifunctional monomer according to claim 12 , wherein A is independently selected from a polybutadienyl linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, a polycarbonate linking group, a polytetrahydrofuran linking group, C 3 -C 6 cycloalkyl linking group, or a triol linking group.

14. A multifunctional monomer according to claim 12 , wherein A is independently selected from any isomer of cyclohexane dimethanol, polybutyl tetrahydrofuran, or trimethylol propane.

15. A multifunctional monomer according to claim 12 , wherein A is independently selected from a polybutadienyl linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, a polycarbonate linking group.

16. A multifunctional monomer according to claim 12 wherein A is independently selected from a C 3 -C 6 cycloalkyl linking groups.

17. A multifunctional monomer according to claim 12 , wherein A is independently selected from a polyester linking group and the polyester linking group is selected from copolymers containing styrene, acrylonitrile, ethers, and ketones that contain ester functionality to allow ester interchange.

18. The multifunctional monomer according to claim 12 , wherein each instance Q is —O—.

19. The multifunctional monomer according to claim 12 , wherein each instance Q is a direct bond.

20. A multifunctional monomer according to claim 12 , wherein R 1 and R 2 are selected from C 1-6 alkyl or a C 3 -C 6 cycloalkyl.

Assignees

• Sirrus Inc

Inventors

• Malofsky Bernard M
• Malofsky Adam G
• Dey Tanmoy
• Ellison Matthew M
• Hines Larry

Classifications

• C07C2601/14

  The ring being saturated · CPC title

• C08K3/013

  Fillers, pigments or reinforcing additives · CPC title

• C08F128/06

  by a heterocyclic ring containing sulfur · CPC title

• C07C67/03

  by reacting an ester group with a hydroxy group · CPC title

• C07C49/794

  having unsaturation outside an aromatic ring · CPC title