Self-assembled elastomers with molecularly encoded tissue-like softness, strain-adaptive stiffening and coloration
View Patent ↗The invention generally relates to linear-bottlebrush-linear copolymer blocks and methods of making and using same. The disclosed copolymer blocks can be useful in, for example, the formation of polymer networks that replicate biological stress-strain behavior. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.
1. A copolymer block comprising a first linear polymer block, a brush-like polymer block, and a second linear polymer block, wherein the brush-like polymer block is positioned between the first and second linear polymer blocks, and wherein each linear block is amorphous.
2. The copolymer block of claim 1 , wherein each linear block is either a methacrylate derivative, an acrylate derivative, a styrene derivative, or a norbornene derivative.
3. The copolymer block of claim 1 , wherein each linear block is independently selected from poly(methyl methacrylate), poly(benzyl methacrylate), polystyrene, poly(vinyl acetate), polycarbonate, and poly(oligo(ethylene glycol) monomethyl ether methacrylate).
4. The copolymer block of claim 1 , wherein the brush-like polymer block comprises the reaction product of:
a) a first monomer having a structure represented by a formula:
wherein R 1 is a structure represented by a formula selected from:
wherein R 10 , when present, is selected from hydrogen and methyl;
wherein R 2 is a first linear polymer residue; and
b) a diluent monomer.
5. The copolymer block of claim 4 , wherein the first linear polymer residue is a residue of a polymer selected frompoly(butyl acrylate), poly(butyl methacrylate), poly(butyl norbornene), polystyrene, polydimethylsiloxane, and polyethylene glycol.
6. The copolymer block of claim 4 , wherein the second linear polymer residue is a residue of a polymer selected from polydimethylsiloxane, polycaprolactone, and poly(butyl acrylate).
7. The copolymer block of claim 4 , wherein the diluent monomer is selected from an alkyl acrylate monomer, a methacrylate monomer, and a norbornene monomer.
8. The copolymer block of claim 1 , wherein the brush-like polymer block comprises at least one residue having a structure represented by a formula selected from:
wherein r is an integer selected from 2 to 800;
wherein L is an active site of polymerization or a residue of a radical initiator;
wherein Q is an active site of polymerization or a residue of a radical initiator;
wherein each occurrence of R 20 is independently selected from a first linear polymer residue and a diluent monomer residue,
provided that at least one occurrence of R 20 is a first linear polymer residue and at least one occurrence of R 20 is a diluent monomer residue; and
wherein each occurrence of R 21 , when present, is independently selected from hydrogen and methyl.
9. The copolymer block of claim 1 , wherein the brush-like polymer block is a polydimethylsiloxane derivative.
10. The copolymer block of claim 1 , wherein the copolymer block is a tri-block copolymer.
11. The copolymer block of claim 10 , wherein the tri-block copolymer is represented by a formula A-B-A′, wherein A is the first linear polymer block, B is the brush-like polymer block, and A′ is the second linear polymer block.
12. A polymer network comprising a plurality of the copolymer blocks of claim 1 .
13. The polymer network of claim 12 , wherein the polymer network has been formed as a medical device.
14. The polymer network of claim 13 , wherein the medical device is selected from an implant, a microneedle array, a wound dressing pad, a tissue adhesive, a tissue sealant, a dermal filler, a vascular graft, or a catheter.
15. The polymer network of claim 12 , wherein the polymer network has been formed as a coating, a gasket, or an adhesive layer.
16. An article comprising the polymer network of claim 12 .