Method of preparing a polyrotaxane and polyrotaxane

Patent metadata

Field	Value
Publication number	US-11248092-B2
Application number	US-201716472266-A
Country	US
Kind code	B2
Filing date	Dec 21, 2017
Priority date	Dec 21, 2016
Publication date	Feb 15, 2022
Grant date	Feb 15, 2022

Abstract

In one embodiment the invention relates to a method of preparing a polyrotaxane, said method comprising: performing a radical copolymerization of at least (a) a first polymerizable monomer having a stopper group, and of at least (b) a second polymerizable hydrophobic monomer, wherein said second monomer is complexed by a ring-shaped molecule, and of at least (c) a third polymerizable hydrophilic monomer; wherein during said copolymerization a copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having a stopper group is incorporated into the chain of said copolymer at least partially between the ends thereof, and wherein said stopper groups prevent said ring-shaped molecule from disassembling from the copolymer; and wherein the amount of said first monomer having a stopper group is of from 0.1 mol % to 20 mol % based on 100 mol % of the total amount of polymerizable monomers. In another embodiment the invention relates to a method of preparing a polyrotaxane, said method comprising: performing a radical copolymerization of at least (a) a first polymerizable monomer having a stopper group, and of at least (b) a second polymerizable partially hydrophilic monomer, wherein said second monomer is complexed by a ring-shaped molecule, and wherein said second monomer has a solubility in water at 20° C. of from 5 g/L to 40 g/L; wherein during said copolymerization a copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having a stopper group is incorporated into the chain of said copolymer at least partially between the ends thereof, and wherein said stopper groups prevent said ring-shaped molecule from disassembling from the copolymer; and wherein the amount of said first monomer having a stopper group is of from 0.1 mol % to 20 mol % based on 100 mol % of the total amount of polymerizable monomers. Furthermore, the present invention relates to methods of preparing cross-linked polyrotaxanes and cross-linked polyrotaxanes which can be prepared using such methods. Thus, the present invention also relates to polyrotaxane and crosslinked polyrotaxanes. The invention also relates to products which contain the polyrotaxanes or cross-linked polyrotaxanes or which can be prepared from the polyrotaxanes or the cross-linked polyrotaxanes. The present invention further relates to the use of polyrotaxanes or cross-linked polyrotaxanes in various applications, such as the use as a self-healing material.

First claim

What is claimed is:

1. A polyrotaxane comprising a ring-shaped molecule and a copolymer threading said ring-shaped molecule, wherein said copolymer comprises at least (a) structural units derived from a first polymerizable monomer having a stopper group, at least (b) structural units derived from a second polymerizable hydrophobic monomer and at least (c) structural units derived from a third polymerizable hydrophilic monomer, wherein said structural units derived from the first monomer having a stopper group are incorporated into the chain of said copolymer at least partially between the ends thereof, wherein said stopper groups prevent the ring-shaped compound from disassembling from the copolymer, and wherein the amount of said structural units derived from the first monomer having a stopper group is 0.1 mol % to 20 mol % based on 100 mol % of the total amount of structural units of the copolymer.

2. The polyrotaxane of claim 1 , wherein said copolymer is a random copolymer, wherein said structural units derived from said first polymerizable monomer having a stopper group are incorporated randomly along the chain of said copolymer at least partially between the ends thereof.

3. The polyrotaxane of claim 1 , wherein said ring-shaped molecule is selected from the group consisting of a cyclodextrin, a cyclodextrin derivative, and any combination thereof.

4. The polyrotaxane of claim 1 , wherein said first monomer having a stopper group has a molecular weight of from 70 g/mol to 1000 g/mol.

5. The polyrotaxane of claim 1 , wherein said first monomer having a stopper group is selected from the group consisting of myrcene, an aromatic vinyl monomer, N-isopropyl (meth)acrylamide, N-vinylcaprolactam, N-vinylcaprolactone, N-vinylimidazole, N-vinylpyrrolidone, a poly(ethylene glycol) (meth)acrylate, an α,ω-bis(meth)acrylate, hydroxyethylmethacrylate, N,N-dimethyl-2-amino-ethylmethacrylate, tetrahydrofurfuryl methacrylate, furfuryl methacrylate, 4-acryloylmorpholine, N-[tris(hydroxymethyl)methyl]acrylamide, styrene, N-isopropylacrylamide, and any combination thereof.

6. The polyrotaxane of claim 1 , wherein said second hydrophobic monomer has a solubility in water at 20° C. of less than 20 g/L.

7. The polyrotaxane of claim 1 , wherein said second hydrophobic monomer is selected from the group of vinyl monomers having a molecular weight less than 120 g/mol, consisting of a 1,3-diene, N-alkyl-acrylamide, an alkylene, and any combination thereof, or wherein said second hydrophobic monomer is selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, chloroprene and any combination thereof.

8. The polyrotaxane of claim 1 , wherein said third hydrophilic monomer has a solubility in water at 20° C. of 45 g/L or more.

9. The polyrotaxane of claim 1 , wherein said third hydrophilic monomer has a molecular weight less than 120 g/mol, or wherein said third polymerizable hydrophilic is selected from the group consisting of methylacrylate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylonitrile, their derivatives, and any combination thereof.

10. A cross-linked polyrotaxane, wherein a polyrotaxane of claim 1 is chemically or physically cross-linked.

11. The cross-linked polyrotaxane of claim 10 , wherein polyrotaxanes are cross-linked intermolecularly via ring-shaped molecules and a cross-linking agent, or wherein the polyrotaxanes are cross-linked intermolecularly via ring-shaped molecules modified with a group having a cross-linkable moiety.

12. The cross-linked polyrotaxane of claim 10 , wherein said cross-linked polyrotaxane is a gel or a slide-ring gel.

13. A hardened material obtained by heating a polyrotaxane according to claim 1 in the absence of any cross-linking agent at temperatures between 80° C. and 150° C.

Assignees

• Univ Saarland

Inventors

• Ali Budiman
• Becker-Willinger Carsten
• Heppe Gisela
• Mueller Nina
• De Oliveira Peter-William
• Wenz Gerhard
• Kali Gergely
• Eisenbarth Harley
• Hero Devid
• Hafner David
• Hilschmann Jessica

Classifications

• C08G83/007 Primary

  Polyrotaxanes; Polycatenanes · CPC title

• C08L31/04

  Homopolymers or copolymers of vinyl acetate · CPC title

• C08F2438/03

  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] · CPC title

• C08F218/08

  Vinyl acetate · CPC title

• C08J3/24 Primary

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title