# US 11,111,330 B2 · Synthesis of multiphase self-healing polymers from commodity monomers

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- Number: US 11,111,330 B2
- Document ID: US11111330B2
- Status: Granted
- Kind: B2
- Application number: 15/736,210
- Filed: 2016-06-20
- Published: 2018-06-21
- Granted: 2021-09-07
- Earliest claimed: 2015-06-24
- Assignees: The Regents of the University of California
- Applicants: The Regents of the University of California
- Inventors: Zhibin Guan; Aaron M. Kushner
- Web page: https://patentgrep.com/patent/US11111330B2

## CPC

- C08F 257/02: on to polymers of styrene or alkyl-substituted styrenes
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A self-healing polymer material that includes a multiphase copolymer, and a method of making the copolymer, are provided. The multiphase copolymer includes one or more hydrogen bond-forming copolymer segments, each segment including a polymerized acrylamide monomer and a polymerized acrylic monomer. The polymerized acrylamide monomer includes functional groups that form hydrogen bonds in the multiphase copolymer, and is present in the one or more copolymer segments in an amount sufficient for self-healing of the multiphase copolymer.

## Claims

### Claim 1

A self-healing polymer material comprising a multiphase copolymer comprising one or more hydrogen bond-forming copolymer segments, each hydrogen bond-forming copolymer segment comprising a polymerized acrylamide monomer and a polymerized acrylic monomer, the polymerized acrylic monomer being a methacrylate monomer or an acrylate monomer, or a combination thereof,
wherein the polymerized acrylamide monomer comprises functional groups that form hydrogen bonds in the multiphase copolymer, and wherein the multiphase copolymer further comprises polymerized styrenic segments forming glassy domains in the multiphase copolymer.

### Claim 2 (depends on 1)

The polymer material of claim 1, wherein the multiphase copolymer is a branched copolymer.

### Claim 3 (depends on 2)

The polymer material of claim 2, wherein the branched copolymer is a graft or brush copolymer comprising the one or more hydrogen bond-forming copolymer segments attached to a polymer backbone, or is a star copolymer comprising the one or more hydrogen bond-forming copolymer segments attached to a core.

### Claim 4 (depends on 1)

The polymer material of claim 1, wherein the polymerized styrenic segments are formed from a styrenic monomer selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, a halogenated styrene, an alkoxystyrene, or a vinylbenzoate ester, and combination thereof.

### Claim 5 (depends on 1)

The polymer material of claim 1, wherein the acrylic monomer of the hydrogen bond-forming copolymer segments is butyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, or butyl methacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-methlxyethyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl acrylate, tetrahydrofurfryl acrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, 2-hydroxymethyl methacrylate, or 2-hydroxypropyl methacrylate, or a combination thereof.

### Claim 6

A self-healing polymer material comprising a multiphase copolymer comprising one or more hydrogen bond-forming copolymer segments, each segment comprising a polymerized acrylamide monomer and a polymerized acrylic monomer, the polymerized acrylic monomer being a methacrylate monomer or an acrylate monomer, or a combination thereof,
wherein the polymerized acrylamide monomer comprises functional groups that form hydrogen bonds in the multiphase copolymer, and wherein the multiphase copolymer is a branched copolymer.

### Claim 7 (depends on 6)

The polymer material of claim 6, wherein the branched copolymer is a graft or brush copolymer comprising the one or more hydrogen bond-forming copolymer segments attached to a polymer backbone, or is a star copolymer comprising the one or more hydrogen bond-forming copolymer segments attached to a core.

### Claim 8 (depends on 6)

The polymer material of claim 6, wherein the multiphase copolymer comprises polymerized styrenic monomer segments or polymerized acrylic monomer segments forming glassy domains in the multiphase copolymer.

### Claim 9 (depends on 8)

The polymer material of claim 8, wherein the polymerized styrenic monomer segments are formed from a styrenic monomer selected from the group consisting of styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, a halogenated styrene, an alkoxystyrene, or a vinylbenzoate ester, and combinations thereof.

### Claim 10 (depends on 9)

The polymer material of claim 9, wherein the acrylic monomer of the polymerized acrylic monomer segments is a methacrylate monomer or an acrylate monomer, or a combination thereof.

### Claim 11 (depends on 10)

The polymer material of claim 10, wherein the acrylic monomer of the polymerized acrylic monomer segments is butyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, or isobornyl methacrylate, or a combination thereof.

### Claim 12 (depends on 6)

The polymer material of claim 6, wherein the acrylic monomer of the hydrogen bond-forming copolymer segments is butyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, or butyl methacrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-methlxyethyl acrylate, 2-hydroxyethyl acrylate, dimethylaminoethyl acrylate, tetrahydrofurfryl acrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, n-stearyl methacrylate, 2-hydroxymethyl methacrylate, or 2-hydroxypropyl methacrylate, or a combination thereof.