Practical synthesis of multiphase self-healing polymers from commodity monomers

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.

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,   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 or acrylic monomer segments forming glassy domains in the multiphase copolymer.   
     
     
         2 . The polymer material of  claim 1 , wherein the multiphase copolymer is a linear copolymer. 
     
     
         3 . The polymer material of  claim 1 , wherein the multiphase copolymer is a branched copolymer. 
     
     
         4 - 5 . (canceled) 
     
     
         6 . The polymer material of  claim 1 , wherein 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, or any combination thereof. 
     
     
         7 . The polymer material of  claim 1 , wherein the acrylic monomer of acrylic monomer segments is a methacrylate monomer or an acrylate monomer, or a combination thereof. 
     
     
         8 . The polymer material of  claim 7 , 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. 
     
     
         9 . The polymer material of  claim 1 , wherein the polymerized acrylamide monomer is acrylamide, (meth)acrylamide, ethyl hexyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dimethylaminohydroxypropyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, a C 1 -C 10  N-alkyl acrylamide, a C 1 -C 10  N-alkyl methacrylamide, N-aryl acrylamide, or N-aryl methacrylamide, or a combination thereof. 
     
     
         10 . The polymer material of  claim 1 , wherein the polymerized acrylic monomer of the hydrogen bond-forming copolymer segments is a methacrylate monomer or an acrylate monomer, or a combination thereof. 
     
     
         11 . The polymer material of  claim 10 , 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. 
     
     
         12 . A method of preparing a self-healing multiphase copolymer, comprising
 connecting one or more hydrogen bond-forming copolymer segments to a polymer segment by polymerization, each copolymer segment comprising a polymerized acrylamide monomer and a polymerized acrylic monomer, wherein the polymerized acrylamide monomer comprises functional groups that form hydrogen bonds in the self-healing multiphase copolymer, and wherein the self-healing multiphase copolymer further comprises polymerized styrenic monomer segments or acrylic monomer segments forming glassy domains in the self-healing multiphase copolymer, and   wherein the polymerized acrylamide monomer comprises functional groups that form hydrogen bonds in the self-healing multiphase copolymer, and is present in the hydrogen bond-forming copolymer segments in an amount sufficient for self-healing of the self-healing multiphase copolymer.   
     
     
         13 . (canceled) 
     
     
         14 . The method of  claim 12 , wherein the self-healing multiphase copolymer is a linear copolymer. 
     
     
         15 . The method of  claim 12 , wherein the self-healing multiphase copolymer is a graft or brush copolymer, and said connecting comprises
 preparing a polymer chain having pendant groups by polymerization of a combination of styrenic monomers,   covalently reacting the pendant groups of the polymer chain to a trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agent to produce a backbone polymer chain comprising trithiocarbonyl groups, wherein the polymer chain forms at least a part of the backbone polymer chain and comprises the trithiocarbonyl groups, and   performing RAFT polymerization with the backbone polymer chain to connect the one or more copolymer segments to the polymer segment.   
     
     
         16 . The method of  claim 15 , wherein the polymerized styrenic monomer segments include a styrenic monomer combination comprising a styrenic monomer and a halogen-functionalized styrenic monomer. 
     
     
         17 . The method of  claim 16 , wherein the styrenic monomer combination is 4-vinylbenzyl chloride and styrene. 
     
     
         18 . The method of  claim 15 , wherein the RAFT agent is potassium ethyl trithiocarbonate. 
     
     
         19 . The method of  claim 12 , wherein the polymerized acrylamide monomer is acrylamide, (meth)acrylamide, ethyl hexyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dimethylaminohydroxypropyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide, C 1 -C 10  N-alkyl acrylamide, C 1 -C 10  N-alkyl methacrylamide, N-aryl acrylamide, or N-aryl methacrylamide, or a combination thereof. 
     
     
         20 . The method of  claim 12 , wherein the polymerized acrylic monomer of the one or more hydrogen bond-forming copolymer segments is a methacrylate monomer or an acrylate monomer, or a combination thereof. 
     
     
         21 . The method of  claim 12 , wherein the polymerized acrylic monomer of the one or more 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.