Catalyst-lean, microcapsule-based self-healing materials via ring-opening metathesis polymerization (romp)

Patent metadata

Field	Value
Publication number	US-2016096956-A1
Application number	US-201414505987-A
Country	US
Kind code	A1
Filing date	Oct 3, 2014
Priority date	Oct 3, 2014
Publication date	Apr 7, 2016
Grant date	—

Abstract

A self-healing composite material includes a polymer matrix, microcapsules filled with a ring-opening metathesis-active monomer (e.g., norbornene, norbornene derivatives such as ethylidene norbornene, or cyclooctadiene), and polymeric particles comprised of a polymer that is soluble in the monomer with which the microcapsules are filled and having catalytic endgroups derived from an olefin metathesis catalyst, such as a Grubbs'-type catalyst. In some embodiments, the polymer having catalytic endgroups is synthesized via solution polymerization of a ring-opening metathesis-active monomer (e.g., norbornene, norbornene derivatives, or cyclooctadiene) in the presence of an olefin metathesis catalyst (e.g., Grubbs' 1st generation catalyst). The polymer having catalytic endgroups may then be processed via a grinding operation, for example, to prepare the small polymeric particles. In other embodiments, the polymeric particles are synthesized directly as microparticles (e.g., microspheres, granules, beads, etc.) utilizing an analogous suspension polymerization.

First claim

What is claimed is:

1 . A method for fabricating a self-healing composite material comprising:
providing polymeric particles comprising a polymer having catalytic endgroups derived from an olefin metathesis catalyst; dispersing the polymeric particles and microcapsules in a base polymer, wherein the microcapsules are filled with a ring-opening metathesis-active monomer, and wherein the polymer of the polymeric particles is soluble in the ring-opening metathesis-active monomer with which the microcapsules are filled.

2 . The method as recited in claim 1 , wherein providing the polymeric particles comprises:
synthesizing the polymer via solution polymerization of at least one ring-opening metathesis-active monomer in the presence of the olefin metathesis catalyst; processing the polymer via a grinding operation to form the polymeric particles.

3 . The method as recited in claim 2 , wherein the olefin metathesis catalyst includes Grubbs' 1st generation catalyst, and wherein the at least one ring-opening metathesis-active monomer is selected from the group consisting of norbornene, ethylidene norbornene, cyclooctadiene, and combinations thereof.

4 . The method as recited in claim 3 , wherein the ring-opening metathesis-active monomer with which the microcapsules are filled is selected from the group consisting of norbornene, norbornene derivatives, cyclooctadiene, and combinations thereof, and wherein the norbornene derivatives are represented by the following formula:

wherein R is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and wherein R′ is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

5 . The method as recited in claim 4 , wherein the at least one ring-opening metathesis-active monomer utilized in synthesizing the polymer includes the same ring-opening metathesis-active monomer with which the microcapsules are filled.

6 . The method as recited in claim 1 , wherein providing the polymeric particles comprises:
synthesizing the polymeric particles via suspension polymerization of at least one ring-opening metathesis-active monomer in the presence of the olefin metathesis catalyst.

7 . The method as recited in claim 6 , wherein the olefin metathesis catalyst includes Grubbs 1st generation catalyst, and wherein the at least one ring-opening metathesis-active monomer is selected from the group consisting of norbornene, ethylidene norbornene, cyclooctadiene, and combinations thereof.

8 . The method as recited in claim 7 , wherein the ring-opening metathesis-active monomer with which the microcapsules are filled is selected from the group consisting of norbornene, norbornene derivatives, cyclooctadiene, and combinations thereof, and wherein the norbornene derivatives are represented by the following formula:

wherein R is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and wherein R′ is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

9 . The method as recited in claim 8 , wherein the at least one ring-opening metathesis-active monomer utilized in synthesizing the polymer includes the same ring-opening metathesis-active monomer with which the microcapsules are filled.

10 . The method as recited in claim 1 , wherein the polymer of the polymeric particles is represented by the following formula:

wherein Ph is a phenyl group, and wherein Cy is a cyclohexyl group.

11 . The method as recited in claim 10 , wherein the ring-opening metathesis-active monomer with which the microcapsules are filled is represented by the following formula:

wherein R is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and wherein R′ is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

12 . The method as recited in claim 11 , wherein the base polymer includes an epoxy polymer.

13 . A self-healing composite material comprising:
a base polymer; microcapsules dispersed in the base polymer, wherein the microcapsules are filled with a ring-opening metathesis-active monomer; polymeric particles dispersed in the base polymer, wherein the polymeric particles comprise a polymer having catalytic endgroups derived from an olefin metathesis catalyst, and wherein the polymer of the polymeric particles is soluble in the ring-opening metathesis-active monomer with which the microcapsules are filled.

14 . The self-healing composite material as recited in claim 13 , wherein the polymer is synthesized via polymerization of at least one ring-opening metathesis-active monomer in the presence of the olefin metathesis catalyst, wherein the olefin metathesis catalyst includes Grubbs' 1st generation catalyst, and wherein the at least one ring-opening metathesis-active monomer is selected from the group consisting of norbornene, ethylidene norbornene, cyclooctadiene, and combinations thereof.

15 . The self-healing composite material as recited in claim 14 , wherein the ring-opening metathesis-active monomer with which the microcapsules are filled is selected from the group consisting of norbornene, norbornene derivatives, cyclooctadiene, and combinations thereof, and wherein the norbornene derivatives are represented by the following formula:

wherein R is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and wherein R′ is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

16 . The self-healing composited material as recited in claim 15 , wherein the at least one ring-opening metathesis-active monomer utilized in synthesizing the polymer includes the same ring-opening metathesis-active monomer with which the microcapsules are filled.

17 . The self-healing composite material as recited in claim 13 , wherein the polymer of the polymeric particles is represented by the following formula:

wherein Ph is a phenyl group, and wherein Cy is a cyclohexyl group.

18 . The self-healing composite material as recited in claim 17 , wherein the ring-opening metathesis-active monomer with which the microcapsules are filled is represented by the following formula:

wherein R is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and wherein R′ is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

19 . The self-healing composite material as recited in claim 18 , wherein the base polymer includes epoxy polymer.

20 . A method for synthesizing a healing polymer in a self-healing composite material comprising a base polymer, microcapsules dispersed in the base polymer, and polymeric particles dispersed in the base polymer, wherein the microcapsules are filled with a ring-opening metathesis-active monomer, wherein the polymeric particles comprise a polymer having catalytic endgroups derived from an olefin metat

Assignees

• IBM

Inventors

• Boday Dylan J
• Mauldin Timothy C

Classifications

• B29C73/22

  the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged · CPC title

• C08G2261/1624

  of Os, Ir, Pt, Ru, Rh or Pd · CPC title

• C08L65/00

  Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers · CPC title

• C08L63/00 Primary

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title