Encapsulated polymerization initiators, polymerization systems and methods using the same

• US 10,087,272 B2
• Filed: 05/13/2017
• Issued: 10/02/2018
• Est. Priority Date: 05/29/2015
• Status: Active Grant

• Current Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Original Assignee: Sirrus, Inc (Nippon Shokubai Company Limited)
• Inventors: Stevenson, Peter Rulon, Palsule, Aniruddha Sudhir, Sullivan, Jeffrey M.
• Primary Examiner(s): Nguyen, Vu A
• Application Number:
  US15/594,590
• Publication Number:
  US 20170247490A1
• Time in Patent Office: 507 Days
• Field of Search: None
• CPC Class Codes: B01J 13/185 in an organic phase
• CPC Class Codes: C08F 222/14 Esters having no free carboxylic acid groups , e.g. dialkyl maleates or fumarates
• CPC Class Codes: C08J 3/241 Preventing premature crosslinking by physical separation of components, e.g. encapsulation
• CPC Class Codes: C08K 3/01 characterized by their specific function
• CPC Class Codes: C08K 5/0008 Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08K 9/10 Encapsulated ingredients
• CPC Class Codes: C08L 27/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C09J 135/02 Homopolymers or copolymers of esters C09J135/06, C09J135/08 take precedence
• CPC Class Codes: C09J 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

Abstract

A polymerizable system includes a curable composition and one or more encapsulated initiator particles. The curable composition can include one or more 1,1-disubstituted alkene compounds and the encapsulated initiator particles can include one or more polymerization initiators encapsulated by a cured composition. The cured composition includes one or more 1,1-disubstituted alkene compounds.

Claims

1. A method of forming encapsulated initiator matrices comprising:

dispersing polymerization initiators in a medium, the polymerization initiators comprising spherical, non-spherical, irregular, angular, textured, or layered particles having an average granulometry of about 0.1 microns to about 1,000 microns; and

adding a first polymerizable composition to the medium, the first polymerizable composition comprising one or more 1,1-disubstituted alkene compounds; and

wherein the first polymerizable composition polymerizes upon contact with the polymerization initiators to form encapsulated initiator matrices.

2. The method of claim 1, further comprising the step of terminating residual polymerization of the first polymerizable composition by adding a first anionic polymerization terminator to the medium.

3. The method of claim 2, wherein the first anionic polymerization terminator comprises a mineral acid, a carboxylic acid, or a combination thereof.

4. The method of claim 1, wherein the one or more 1,1-disubstituted alkene compounds of the first polymerizable composition comprise low Tg 1,1-disubstituted alkene compounds.

5. The method of claim 1, wherein the one or more 1,1-disubstituted alkene compounds of the first polymerizable composition comprise a blend of low Tg 1,1-disubstituted alkene compounds and elevated Tg 1,1-disubstituted alkene compounds.

6. The method of claim 1, wherein the one or more 1,1-disubstituted alkene compounds of the first polymerizable composition are selected from the group consisting of methylene malonates, methylene β

-ketoesters, methylene β

-diketones, dialkyl disubstituted vinyls, dihaloalkyl disubstituted vinyls, monofunctional, difunctional, or multifunctional monomers, oligomers, or polymers thereof, and combinations thereof.

7. The method of claim 1, wherein the first polymerizable composition further comprises one or more plasticizers.

8. The method of claim 1, wherein the medium comprises an aqueous composition.

9. The method of claim 1, wherein the encapsulated initiator particles rupture when about 0.1 psi or more of mechanical force is applied.

10. The method of claim 1, further comprising the step of adding a second polymerizable composition to the medium after forming the encapsulated initiator matrices, the second polymerizable composition polymerizing upon contact with the encapsulated initiator matrices to form a shell layer surrounding the encapsulated initiator matrices.

11. The method of claim 10, wherein the second polymerizable composition comprises one or more 1,1-disubstituted alkene compounds.

12. The method of claim 11, wherein the one or more 1,1-disubstituted alkene compounds of the first polymerizable composition and the one or more 1,1-disubstituted alkene compounds of the second composition are different.

13. The method of claim 12, further comprising the step of terminating residual polymerization of the second polymerizable composition by adding a second anionic polymerization terminator.

14. A method of curing a polymerizable system comprising:

providing a polymerizable system comprising;

a curable composition comprising one or more 1,1-disubstituted alkene compounds; and

one or more encapsulated initiator particles, each of the one or more encapsulated initiator particles comprising;

one or more polymerization initiators substantially encapsulated by a cured composition formed from one or more 1,1-disubstituted alkene compounds, the one or more polymerization initiators comprising spherical, non-spherical, irregular, angular, textured, or layered particles having an average granulometry of about 0.1 microns to about 1,000 microns; and

rupturing the one or more encapsulated initiator particles to initiate polymerization of the curable composition.

15. The method of claim 14, wherein the step of rupturing the one or more encapsulated initiator particles comprises the application of thermal shock or about 5 psi, or more, of mechanical force to the polymerizable system.

16. The method of claim 14, wherein the encapsulated initiator particles are mononuclear or polynuclear encapsulated initiator particles.

17. The method of claim 14, wherein the one or more 1,1-disubstituted alkene compounds of the curable composition and the one or more 1,1-disubstituted alkene compounds of the cured composition are each selected from the group consisting of methylene malonates, methylene β

-ketoesters, methylene β

-diketones, dialkyl disubstituted vinyls, dihaloalkyl disubstituted vinyls, monofunctional, difunctional, or multifunctional monomers, oligomers, or polymers thereof, and combinations thereof.

18. The method of claim 14, wherein the one or more 1,1-disubstituted alkene compounds of the curable composition and the one or more 1,1-disubstituted alkene compounds of the cured composition are different.

19. The method of claim 14, wherein the ratio of the cured composition to the one or more polymerization initiators is a ratio of about 1:

1 to about 2;

1.

20. The method of claim 14, wherein the polymerizable system further comprises one or more of a plasticizer, a stabilizer, a thickening agent, and a thixotropic agent.