Method of preparing a polyrotaxane and polyrotaxane

Patent metadata

Field	Value
Publication number	US-2019322814-A1
Application number	US-201716472266-A
Country	US
Kind code	A1
Filing date	Dec 21, 2017
Priority date	Dec 21, 2016
Publication date	Oct 24, 2019
Grant date	—

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 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 hydrophobic 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.

2 . The method of claim 1 , said method comprising the steps of:
(a) providing a composition comprising a ring-shaped molecule and the first polymerizable monomer having a stopper group; (b) combining the second polymerizable hydrophobic monomer and the third polymerizable hydrophilic monomer with the composition of step (a) and forming a complex of said ring-shaped molecule with said second hydrophobic monomer; and (c) performing a radical copolymerization on the composition of step (b) to form a polyrotaxane;
wherein during said copolymerization a random copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having a stopper group is incorporated randomly along the chain of said copolymer.

3 . 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 partially hydrophilic monomer is complexed by a ring-shaped molecule, and wherein said second partially hydrophilic 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.

4 . The method of claim 3 , wherein said second polymerizable partially hydrophilic monomer has a solubility in water at 20° C. of from 10 g/L to 40 g/L, more preferably of from 15 g/L to 40 g/L, even more preferably of from 20 g/L to 30 g/L.

5 . The method of claim 3 or 4 , said method comprising the steps of:
(a) providing a composition comprising a ring-shaped molecule, the first polymerizable monomer having a stopper group, and the second polymerizable partially hydrophilic monomer, and forming a complex of said ring-shaped molecule with said second partially hydrophilic monomer; and
(b) performing a radical copolymerization on the composition of step (a) to form a polyrotaxane;

wherein during said copolymerization a random copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having a stopper group is incorporated randomly along the chain of said copolymer.

6 . The method of any one of claims 3 to 5 , comprising further copolymerizing at least (c) a third polymerizable hydrophobic monomer.

7 . The method of claim 6 , said method comprising the steps of:
(a) providing a composition comprising a ring-shaped molecule and the first polymerizable monomer having a stopper group; (b) combining the second polymerizable partially hydrophilic monomer and the third polymerizable hydrophobic monomer with the composition of step (a) and forming a complex of said ring-shaped molecule with said second partially hydrophilic monomer; and (c) performing a radical copolymerization on the composition of step (b) to form a polyrotaxane;
wherein during said copolymerization a random copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having a stopper group is incorporated randomly along the chain of said copolymer.

8 . The method of any one of the preceding claims, wherein the amount of said first monomer having a stopper group is of from 0.3 mol % to 18 mol %, more preferably of from 0.5 mol % to 14 mol %, even more preferably of from 0.7 mol % to 10 mol %, still more preferably of from 0.9 mol % to 5 mol %, and most preferably of from 1 mol % to 2.5 mol %, each based on 100 mol % of the total amount of polymerizable monomers.

9 . The method of any one of the preceding claims, wherein the ring-shaped molecule is threaded on the main chain of the copolymer.

10 . The method of any one of claims 2 , and 5 to 9 , wherein the composition provided in step (a) comprises a radical initiator.

11 . The method of any one of claims 2 and 8 to 10 , wherein prior to step (b) a composition of the second polymerizable hydrophobic monomer and the third polymerizable hydrophilic monomer is provided which is then added to the composition provided in step (a).

12 . The method of claim 11 , wherein the composition of the second polymerizable hydrophobic monomer and the third polymerizable hydrophilic monomer further comprises a radical initiator.

13 . The method of any one of claims 7 to 10 , wherein prior to step (b) a composition of the second polymerizable partially hydrophilic monomer and the third polymerizable hydrophobic monomer is provided which is then added to the composition provided in step (a).

14 . The method of claim 13 , wherein the composition of the second polymerizable partially hydrophilic monomer and the third hydrophobic monomer further comprises a radical initiator and/or a chain transfer agent.

15 . The method of any one of claims 2 and 5 to 14 , wherein the composition provided in step (a) is deoxygenated before being subjected to copolymerization.

16 . The method of any one of the preceding claims, wherein the copolymerization is initiated thermally and/or photochemically.

17 . The method of any one of claims 1 , 2 , 8 to 12 and 15 to 16 , wherein the polyrotaxane is a terpolymer obtained by terpolymerization of said first polymerizable monomer having a stopper group, said second polymerizable hydrophobic monomer, wherein said second polymerizable hydrophobic monomer is complexed by a ring-shaped molecule, and said third polymerizable hydrophilic monomer.

18 . The method of any one of claims 6 , 7 , 8 to 10 and 13 to 16 , wherein the polyrotaxane is a terpolymer obtained by terpolymerization of said first polymerizable monomer having a stopper group, said second polymerizable partially hydrophilic monomer, wherein said second polymerizable partially hydrophilic monomer is complexed by a ring-shaped molecule, and said third polymerizable hydrophobic monomer.

19 . The method of any one of the preceding claims, wherein said ring-shaped molecule is selected from the group consisting of a cyclodextrin, a cyclodextrin derivative and any combination thereof.

20 . The method of 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

• C08F220/44

  Acrylonitrile · CPC title

• C08J3/075

  Macromolecular gels · CPC title

• C08F236/04

  conjugated · CPC title

• C08G83/007 Primary

  Polyrotaxanes; Polycatenanes · CPC title

• C08L2312/00

  Crosslinking · CPC title