Self-healing polymer compositions

• US 7,108,914 B2
• Filed: 07/15/2002
• Issued: 09/19/2006
• Est. Priority Date: 07/15/2002
• Status: Expired due to Term

• Current Assignee: Google Technology Holdings LLC (Alphabet Inc.)
• Original Assignee: Motorola, Inc. (Motorola Solutions, Inc.)
• Inventors: Olson, Bill, Scheifer, Steve, Skipor, Andrew
• Primary Examiner(s): LAM, CATHY FONG FONG
• Application Number:
  US10/195,858
• Publication Number:
  US 20040007784A1
• Time in Patent Office: 1,527 Days
• Field of Search: 428/402.21, 428/320.2, 523/204, 523/205, 523/210
• US Class Current: 428/402.21
• CPC Class Codes: B01J 13/02 Making microcapsules or microballoons for medical preparations A61K9/50
• CPC Class Codes: B29C 73/163 Sealing compositions or agents, e.g. combined with propellant agents
• CPC Class Codes: B29C 73/22 the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H01L 2224/29101 the principal constituent melting at a temperature of less than 400°C
• CPC Class Codes: H01L 2224/2919 with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
• CPC Class Codes: H01L 2224/29339 Silver [Ag] as principal constituent
• CPC Class Codes: H01L 2224/32225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/45124 Aluminium (Al) as principal constituent
• CPC Class Codes: H01L 2224/45144 Gold (Au) as principal constituent
• CPC Class Codes: H01L 2224/4554 Coating
• CPC Class Codes: H01L 2224/45611 Tin (Sn) as principal constituent
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48227 connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/73265 Layer and wire connectors
• CPC Class Codes: H01L 2224/8319 Arrangement of the layer connectors prior to mounting
• CPC Class Codes: H01L 2224/83855 Hardening the adhesive by curing, i.e. thermosetting
• CPC Class Codes: H01L 23/145 Organic substrates, e.g. plastic
• CPC Class Codes: H01L 23/293 Organic, e.g. plastic
• CPC Class Codes: H01L 24/29 of an individual layer connector
• CPC Class Codes: H01L 24/32 : of an individual layer connector
• CPC Class Codes: H01L 24/45 : of an individual wire connector
• CPC Class Codes: H01L 24/48 : of an individual wire connector
• CPC Class Codes: H01L 24/73 : Means for bonding being of different types provided for in two or more of groups H01L24/10, H01L24/18, H01L24/26, H01L24/34, H01L24/42, H01L24/50, H01L24/63, H01L24/71
• CPC Class Codes: H01L 24/83 : using a layer connector
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/00012 : Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00014 : the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2924/01005 : Boron [B]
• CPC Class Codes: H01L 2924/01006 : Carbon [C]
• CPC Class Codes: H01L 2924/01011 : Sodium [Na]
• CPC Class Codes: H01L 2924/01013 : Aluminum [Al]
• CPC Class Codes: H01L 2924/01014 : Silicon [Si]
• CPC Class Codes: H01L 2924/01015 : Phosphorus [P]
• CPC Class Codes: H01L 2924/01019 : Potassium [K]
• CPC Class Codes: H01L 2924/0102 : Calcium [Ca]
• CPC Class Codes: H01L 2924/01023 : Vanadium [V]
• CPC Class Codes: H01L 2924/01027 : Cobalt [Co]
• CPC Class Codes: H01L 2924/01029 : Copper [Cu]
• CPC Class Codes: H01L 2924/01033 : Arsenic [As]
• CPC Class Codes: H01L 2924/01039 : Yttrium [Y]
• CPC Class Codes: H01L 2924/01041 : Niobium [Nb]
• CPC Class Codes: H01L 2924/01044 : Ruthenium [Ru]
• CPC Class Codes: H01L 2924/01047 : Silver [Ag]
• CPC Class Codes: H01L 2924/01049 : Indium [In]
• CPC Class Codes: H01L 2924/0105 : Tin [Sn]
• CPC Class Codes: H01L 2924/01075 : Rhenium [Re]
• CPC Class Codes: H01L 2924/01076 : Osmium [Os]
• CPC Class Codes: H01L 2924/01078 : Platinum [Pt]
• CPC Class Codes: H01L 2924/01079 : Gold [Au]
• CPC Class Codes: H01L 2924/01082 : Lead [Pb]
• CPC Class Codes: H01L 2924/014 : Solder alloys
• CPC Class Codes: H01L 2924/0665 : Epoxy resin
• CPC Class Codes: H01L 2924/07802 : not being an ohmic electrical conductor
• CPC Class Codes: H01L 2924/09701 : Low temperature co-fired ceramic [LTCC]
• CPC Class Codes: H01L 2924/12044 : OLED
• CPC Class Codes: H01L 2924/14 : Integrated circuits
• CPC Class Codes: H01L 2924/181 : Encapsulation
• CPC Class Codes: H01L 2924/19042 : being an inductor
• CPC Class Codes: H01L 2924/3512 : Cracking
• CPC Class Codes: Y10T 428/249995 : Constituent is in liquid form
• CPC Class Codes: Y10T 428/2985 : Solid-walled microcapsule from synthetic polymer

Abstract

A self-healing polymer composition 10 contains a polymer media 12 and a plurality of microcapsules of flowable polymerizable material 16 dispersed in the polymer media 12, where the microcapsules of flowable polymerizable material 16 contain a flowable polymerizable material 15 and have an outer surface 142 upon which at least one polymerization agent 13 is chemically attached. The microcapsules 16 are effective for rupturing with a failure of the polymeric media 12, and the flowable polymerizable material 15 reacts with the polymerization agent 13 when the polymerizable material 15 makes contact with the polymerization agent 13 upon rupture of the microcapsules 14. There is also provided a method of using the self-healing polymeric composition 10 to repair fractures in polymers, as well as articles of manufacture including the self-healing system, and the microencapsulated polymerizable particles 16 themselves.

Claims

1. A self-healing polymer composition comprising:

a polymer media; and

a plurality of microcapsules of flowable polymerizable material dispersed in the polymer media,

the microcapsules of flowable polymerizable material including microcapsules, flowable polymerizable material inside the microcapsules and at least one polymerization agent chemically attached to an outer surface of at least some of the microcapsules via a molecular bridging unit, the microcapsules effective for rupturing with a failure of the polymeric media and the flowable polymerizable material reacting with the polymerization agent upon rupture of the microcapsules.

2. The self-healing composition of claim 1, further including solvent inside the microcapsule in an amount effective to facilitate flow of the polymerizable material upon rupture of the microcapsule.

3. The self-healing composition of claim 1, wherein the microcapsule includes a metal film on its outer surface, the metal film effective for chemically attaching a polymerization agent to the microcapsule.

4. The self-healing composition of claim 3 further including a matrix layer comprising thiol moieties chemically attached to the metal film, a linear molecule of the molecular bridging unit having a backbone and opposite first and second ends attached from the first end thereof to the thiol moieties of the matrix layer and including carbon-carbon double bonds along the backbone and at the second end having a group selected from a norbornenyl group, a norbornenyl derivative group, and combinations thereof, which incorporates the polymerization agent.

5. The self-healing composition of claim 1, wherein the molecular bridging unit comprises a linear molecule chemically attached to the outer surface of the microcapsule, and wherein the polymerization agent comprises a derivative of BF₃ chemically attached to the outer surface of the microcapsule through the linear molecule.

6. The self-healing composition of claim 1, wherein the polymerization agent is selected from the group consisting of derivatives of aluminum (III), titanium (IV), tin (V), and mixtures thereof.

7. The self-healing composition of claim 1 wherein the microcapsule includes a shell defining an interior space with the flowable polymerizable material therein.

8. The self-healing composition of claim 1 wherein the microcapsule shell comprises a material selected from the group consisting of hydrous metal oxide, silica, silicate, carbon, polymer, and mixtures thereof.

9. The self-healing composition of claim 1 wherein the outer surface of the microcapsule is treated with a bonding agent effective for chemically attaching the polymerization agent to the microcapsule.

10. The self-healing composition of claim 9 wherein the bonding agent is a silanization agent.

11. The self-healing composition of claim 1 wherein the flowable polymerizable material is selected from the group consisting of norbornene, alkyl-substituted norbornene derivatives, alkoxysilynorbornenes, dicyclopentadiene, dicyclopentadiene oligomers, dicyclopentadiene copolymers, and mixtures thereof.

12. The self-healing composition of claim 1 wherein the flowable polymerizable material is selected from the group consisting of trimethoxysilylnorbornene, norbornene, ethyl norbornene, propylnorbornene, butylnorbornene, hexylnorbornene, dicyclopentadiene, and mixtures thereof.

13. The self-healing composition of claim 1 wherein the polymerization agent is selected from the group consisting of a ruthenium complex, an osmium complex, an indium complex, and mixtures thereof.

14. The self-healing composition of claim 1 wherein the polymerization agent is selected from the group consisting of a ruthenium complex derived from RuCI₃, K₂RuCI₅, Ru(H₂O)₆-(tos)₂ where tos is toluene sulfonate, and mixtures thereof.

15. The self-healing composition of claim 1 wherein the polymer media is selected from the group consisting of thermoset, thermoplastic, elastomeric, and mixtures thereof.