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

• US 9,828,324 B2
• Filed: 09/29/2015
• Issued: 11/28/2017
• Est. Priority Date: 10/20/2010
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Sullivan, Jeffrey M., Malofsky, Adam G., Malofsky, Bernard M., Dey, Tanmoy
• Primary Examiner(s): Butcher, Robert T
• Application Number:
  US14/868,795
• Publication Number:
  US 20160068618A1
• Time in Patent Office: 791 Days
• Field of Search: None
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 45/75 Reactions with formaldehyde
• CPC Class Codes: C07C 49/203 with only carbon-to-carbon double bonds as unsaturation
• CPC Class Codes: C07C 49/227 containing halogen
• CPC Class Codes: C07C 49/557 having unsaturation outside the rings
• CPC Class Codes: C07C 49/794 having unsaturation outside an aromatic ring
• CPC Class Codes: C07C 49/796 polycyclic
• CPC Class Codes: C07C 49/80 containing halogen
• CPC Class Codes: C07C 49/84 containing ether groups, groups, groups, or groups
• CPC Class Codes: C07D 307/46 Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
• CPC Class Codes: C07D 333/22 Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

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).

Claims

1. A polymerizable composition comprising:

at least one methylene beta-diketone monomer having the structural formula;

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 R₁—

C(O)—

C—

C(O)—

R₂, 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;

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 R₁—

C(O)—

C—

C(O)—

R₂, 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 R₁—

C(O)—

C—

C(O)—

R₂, 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;

20. The polymerizable composition of claim 19, 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.

21. The polymerizable composition of claim 19, 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.

22. The polymerizable composition of claim 21, wherein the polymerizable composition is an adhesive, a coating, or a sealant.

23. The polymerizable composition of claim 21, 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.

24. The polymerizable composition of claim 21, wherein the at least one stabilizer includes the vapor phase stabilizer selected from hydroquinone, methyl hydroquinone, butylated hydroxytoluene, butylated hydroxyanisole.

25. The polymerizable composition of claim 19, wherein the methylene beta-diketone monomer is formed as a reaction product of a 1,3-disubstituted-propane-1,3-dione represented by R₁—

C(O)—

C—

C(O)—

R₂, and a source of formaldehyde.

26. The polymerizable composition of claim 25, 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.

27. The polymerizable composition of claim 19, wherein the methylene beta-diketone monomer has a structural formula selected from the group consisting of:

28. A polymer prepared from the polymerizable composition of claim 19.

29. The polymerizable composition of claim 19, 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.