Self-healing polymer compositions

• US 20040007784A1
• Filed: 07/15/2002
• Published: 01/15/2004
• Est. Priority Date: 07/15/2002
• Status: Active Grant

• Current Assignee: Google Technology Holdings LLC (Alphabet Inc.)
• Original Assignee: Motorola, Inc. (Motorola Solutions, Inc.)
• Inventors: Olson, Bill, Skipor, Andrew, Scheifer, Steve
• Granted Patent: US 7,108,914 B2
• Time in Patent Office: Days
• US Class Current: 257/788
• 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 containing 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 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 microencapsulated polymerizable composition comprising:

a microcapsule;

a flowable polymerizable material inside the microcapsule; and

at least one polymerization agent associated with an outer surface of the microcapsule,

the polymerization agent effective for inducing polymerization of the flowable polymerizable material upon rupture of the microcapsule and contact between the polymerization agent and the flowable polymerizable material.

2. The microencapsulated polymerizable composition of claim 1 wherein the microcapsule includes a shell defining an interior space with the flowable polymerizable material therein.

3. The microencapsulated polymerizable composition of claim 2 wherein the microcapsule shell comprises a material selected from the group consisting of hydrous metal oxide, silica, silicate, carbon, polymer, and mixtures thereof.

4. The microencapsulated polymerizable composition of claim 1 wherein the outer surface of the microcapsule is treated with a bonding agent effective for attaching the polymerization agent to the microcapsule.

5. The microencapsulated polymerizable composition of claim 4 wherein the bonding agent is a silanization agent.

6. The microencapsulated polymerizable 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.

7. The microencapsulated polymerizable composition of claim 1 wherein the microcapsule includes a metal film on its outer surface, the metal film effective for attaching a polymerization agent to the microcapsule.

8. The microencapsulated polymerizable composition of claim 7 further including a matrix layer on the metal film present from the contact of alkanethiol thereon, a linear molecule having a backbone and opposite first and second ends attached from the first end thereof to 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.

9. The microencapsulated polymerizable 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.

10. The microencapsulated polymerizable composition of claim 1, wherein the flowable polymerizable material is selected from the group consisting of triethoxysilylnorbornene, norbornene, ethyl norbornene, propylnorbornene, butylnorbornene, hexylnorbornene, dicyclopentadiene, and mixtures thereof.

11. The microencapsulated polymerizable 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.

12. The microencapsulated polymerizable composition of claim 1 wherein the polymerization agent comprises ruthenium complex derived from RuCl₃, K₂RuCl₅, or Ru(H₂O)₆-(tos)₂ where tos is toluene sulfonate, or a mixture thereof.

13. The microencapsulated polymerizable composition of claim 1 further comprising a linear molecule attached to the outer surface of the microcapsule, and wherein the polymerization agent comprises a derivative of BF₃ attached to the linear molecule.

14. The microencapsulated polymerizable 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.

15. 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 attached to an outer surface of at least some of the microcapsules, the microcapsules effective for rupturing with a failure of the polymeric media and the polymerizable material reacting with the polymerization agent upon rupture of the microcapsules.

16. The self-healing composition of claim 15 wherein the microcapsule includes a shell defining an interior space with the flowable polymerizable material therein.

17. The self-healing composition of claim 15 wherein the microcapsule shell comprises a material selected from the group consisting of hydrous metal oxide, silica, silicate, carbon, polymer, and mixtures thereof.

18. The self-healing composition of claim 15 wherein the outer surface of the microcapsule is treated with a bonding agent effective for attaching the polymerization agent to the microcapsule.

19. The self-healing composition of claim 18 wherein the bonding agent is a silanization agent.

20. The self-healing composition of claim 15 wherein the microcapsule further comprises a metal film on its outer surface, the metal film effective for bonding polymerization agent to the microcapsule.

21. The self-healing composition of claim 15 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.

22. The self-healing composition of claim 15 wherein the flowable polymerizable material is selected from the group consisting of trimethoxysilylnorbornene, norbornene, ethyl norbornene, propylnorbornene, butylnorbornene, hexylnorbornene, dicyclopentadiene, and mixtures thereof.

23. The self-healing composition of claim 15 wherein the polymerization agent is selected from the group consisting of a ruthenium complex, an osmium complex, an indium complex, and mixtures thereof.

24. The self-healing composition of claim 15 wherein the polymerization agent is selected from the group consisting of a ruthenium complex derived from RuCl₃, K₂RuCl₅, Ru(H₂O)₆-(tos)₂ where tos is toluene sulfonate, and mixtures thereof.

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

26. A process for making a self-healing composition comprising:

dispersing a plurality of microcapsules of flowable polymeric material in a polymer media,

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

27. The process of claim 26 wherein the microcapsule polymerization agent includes a shell defining an interior space with the flowable polymeric material therein.

28. The process of claim 27 wherein the microcapsule shell comprises a material selected from the group consisting of hydrous metal oxide, silica, silicate, carbon, polymer, and mixtures thereof.

29. The process of claim 26 wherein the outer surface of the microcapsule is treated with a bonding agent effective for attaching the polymerization agent to the microcapsule.

30. The process of claim 29 wherein the bonding agent is a silanization agent.

31. The process of claim 26 wherein a metal film is bonded to the outer surface of the microcapsule, the metal film effective for attaching polymerization agent to the microcapsule.

32. The process of claim 31 wherein the attaching of the polymerization agent being conducted by functionalizing the metal film by contacting the metal film with an alkanethiol, followed by contacting is the coupling agent comprises a thiol group having norbornene groups, norbornene derivative groups, or combinations thereof, in which the coupling agent is selected from at least one of 5-(bicycloheptenyl)trichlorosilane or 5-(bicycloheptenyl)triethoxysilane, wherein the surface treated microcapsules having been reacted with the polymerization agent such that a strained ring of the norbornene groups or the norbornene derivative groups has reacted with the polymerization agent such that polymerization agent opened the rings and has been attached to the coupling agent via remaining broken norbornene groups or norbornene derivative groups.

33. The process of claim 26 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.

34. The process of claim 26 wherein the flowable polymerizable material is selected from the group consisting of trimethoxysilylnorbornene, norbornene, ethyl norbornene, propylnorbornene, butylnorbornene, hexylnorbornene, dicyclopentadiene, and mixtures thereof.

35. The process of claim 26 wherein the polymerization agent is selected from the group consisting of a ruthenium complex, an osmium complex, and an indium complex, and mixtures thereof.

36. The process of claim 26 wherein the polymerization agent is a ruthenium complex derived from RuCl₃, K₂RuCl₅, Ru(H₂O)₆-(tos)₂ where tos is toluene sulfonate, or a mixture thereof.

37. The process of claim 26 wherein the polymer is selected from the group consisting of thermoset, thermoplastic, elastomeric, and mixtures thereof.

38. An article of manufacture comprising a self-healing composition, the self-healing composition including a polymer media;

and

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

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

39. The article of manufacture of claim 38 wherein the article of manufacture is selected from the group consisting of electronic packages, electronic encapsulants, electronic die attach, plastic packaging, structural composites, windows, floatation devices, pneumatic tire parts, adhesives, paints, sealants, impregnating resins, finishes, coatings, and mixtures thereof.

40. An electronic package comprising:

a printed circuit board;

a semiconductor device attached to the printed circuit board by an adhesive; and

an encapsulant covering the semiconductor device and at least portions of the printed circuit board,

at least one of the adhesive or encapsulant including a microencapsulated polymerizable composition comprising;

a microcapsule;

a flowable polymerizable material inside the microcapsule; and

at least one polymerization agent attached to an outer surface of the microcapsule,

the polymerization agent effective for inducing polymerization of the flowable polymerizable material upon rupture of the microcapsule and contact between the polymerization agent and the flowable polymerizable material.

41. A printed circuit board comprising a metal circuit pattern disposed on a board that includes a plurality of layers of fiber reinforced resin, wherein the resin includes a microencapsulated polymerizable composition comprising:

a microcapsule;

a flowable polymerizable material inside the microcapsule; and

at least one polymerization agent attached to an outer surface of the microcapsule,

the polymerization agent effective for inducing polymerization of the flowable polymerizable material upon rupture of the microcapsule and contact between the polymerization agent and the flowable polymerizable material.

42. A microencapsulated polymerizable composition comprising:

a microcapsule;

a flowable polymerizable material inside the microcapsule, the flowable polymerizable material selected from the group consisting of norbornene, alkyl-substituted norbornene derivatives, alkoxysilynorbornenes, dicyclopentadiene, dicyclopentadiene oligomers, dicyclopentadiene copolymers, and mixtures thereof; and

at least one polymerization agent attached to an outer surface of the microcapsule, the polymerization agent selected from the group consisting of a ruthenium complex, an osmium complex, an indium complex, and mixtures thereof,

the polymerization agent effective for inducing polymerization of the flowable polymerizable material upon rupture of the microcapsule and contact between the polymerization agent and the flowable polymerizable material.