Method of preparing a polyrotaxane and polyrotaxane

Patent metadata

Field	Value
Publication number	US-10954331-B2
Application number	US-201615736863-A
Country	US
Kind code	B2
Filing date	Jun 16, 2016
Priority date	Jun 17, 2015
Publication date	Mar 23, 2021
Grant date	Mar 23, 2021

Abstract

The present 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 monomer, wherein said second monomer is complexed by a ring-shaped molecule; 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.

The present invention also relates to polyrotaxanes which can be prepared by using such a method.
The present invention further relates to cross-linked polyrotaxanes, products which contain polyrotaxanes or cross-linked polyrotaxanes or which can be prepared from polyrotaxanes or cross-linked polyrotaxanes, and the use of polyrotaxanes or cross-linked polyrotaxanes.

First claim

What is claimed is:

1. A cross-linked polyrotaxane, wherein molecules of said polyrotaxane are cross-linked intermolecularly via ring-shaped molecules and a cross-linking agent; wherein said polyrotaxane comprises a ring-shaped molecule and a copolymer threading said ring-shaped molecule, wherein said copolymer is a non-ionic copolymer comprising at least (a) structural units derived from a first polymerizable monomer having a stopper group and at least (b) structural units derived from a second polymerizable 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 molecule 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;
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; and
wherein said cross-linking agent is selected from the group consisting of a diisocyanate, a blocked diisocyanate, a diisothiocyanate, a bisepoxide, cyanuric chloride, divinylsulfone, and any combination thereof.

2. A method of preparing the cross-linked polyrotaxane of claim 1 , said method comprising:
(i) providing the polyrotaxane, comprising:
performing a radical copolymerization of at least (a) the first polymerizable monomer having a stopper group, and of at least (b) the second polymerizable monomer, wherein said second monomer is complexed by the ring-shaped molecule;
wherein during said copolymerization the copolymer threading said ring-shaped molecule is formed, wherein during said copolymerization said first monomer having the 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;
wherein the amount of said first monomer having the stopper group is of from 0.1 mol % to 20 mol % based on 100 mol % of the total amount of polymerizable monomers;
wherein said copolymer is a non-ionic copolymer; and
wherein said copolymer is the random copolymer, wherein said structural units derived from said first polymerizable monomer having the stopper group are incorporated randomly along the chain of said copolymer at least partially between the ends thereof; and

(ii) cross-linking molecules of said copolymer, wherein said cross-linking comprises intermolecular cross-linking of polyrotaxanes by cross-linking of ring-shaped molecules using a cross-linking agent selected from the group consisting of a diisocyanate, a blocked diisocyanate, a diisothiocyanate, a bisepoxide, cyanuric chloride, divinylsulfone, and any combination thereof.

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

4. The method of claim 3 , wherein the composition provided in step (a) comprises a radical initiator; or
wherein polymerization is accelerated by adding an accelerator for radical initiation.

5. The method of claim 2 , wherein the amount of said first monomer having the stopper group is of from 0.5 mol % to 18 mol % based on 100 mol % of the total amount of polymerizable monomers.

6. The method of claim 2 , wherein said ring-shaped molecule is selected from the group consisting of a cyclodextrin, a cyclodextrin derivative and any combination thereof.

7. The method of claim 2 , wherein said first monomer has a molecular weight of from 70 g/mol to 1000 g/mol.

8. The method of claim 2 , 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-vinylimidazole, a poly(ethylene glycol) (meth)acrylate, an α,ω-bis(meth)acrylate, and any combination thereof; or
wherein said first monomer having the stopper group is selected from the group consisting of optionally substituted styrene, optionally substituted styrenesulfonic acid, optionally substituted vinylpyridine, optionally substituted divinyl benzene, and any combination thereof.

9. The method of claim 2 , wherein said second monomer is a hydrophobic monomer; or
wherein said second monomer is selected from the group of vinyl monomers having a molecular weight less than 120 g/mol consisting of a 1,3-diene, a 1,3,5-triene, a (meth)acrylate, a vinyl ester, a vinyl-ether, (meth)acrylonitrile, (meth)acrylic acid, (meth)acrylamide, and any combination thereof.

10. The method of claim 9 , wherein said vinyl ester is vinyl acetate.

11. The method of claim 2 , wherein said copolymerization is performed in an aqueous medium; or
wherein said copolymerization is performed using a water-soluble radical initiator; or
wherein said copolymerization is carried out using a chain transfer agent.

12. The cross-linked polyrotaxane of claim 1 , wherein the amount of said structural units derived from the first monomer having the stopper group is 0.5 mol % to 18 mol % based on 100 mol % of the total amount of structural units of the copolymer.

13. The cross-linked 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.

14. The cross-linked polyrotaxane of claim 1 , wherein said first monomer has a molecular weight of from 70 g/mol to 1000 g/mol.

15. The cross-linked polyrotaxane of claim 1 , wherein said first monomer having the stopper group is selected from the group consisting of myrcene, an aromatic vinyl monomer, N-isopropyl (meth)acrylamide, N-vinylcaprolactam, N-vinylimidazole, a poly(ethylene glycol) (meth)acrylate, an α,ω-bis(meth)acrylate, and any combination thereof; or
wherein said first monomer having the stopper group is selected from the group consisting of optionally substituted styrene, optionally substituted styrenesulfonic acid, optionally substituted vinylpyridine, optionally substituted divinyl benzene, and any combination thereof.

16. The cross-linked polyrotaxane of claim 1 , wherein said second monomer is a hydrophobic monomer; or
wherein said second monomer is selected from the group of vinyl monomers having a molecular weight less than 120 g/mol consisting of a 1,3-diene, a 1,3,5-triene, a (meth)acrylate, a vinyl ester, a vinyl-ether, (meth)acrylonitrile, (methacrylic) acid, (meth)acrylamide, and any combination thereof.

17. The cross-linked polyrotaxane of claim 16 , wherein said vinyl ester is vinyl acetate.

18. A dispersion comprising metal particles and/or metal oxide particles and a cross-linked polyrotaxane according to claim 1 .

Assignees

• Univ Saarland

Inventors

• Eisenbarth Harley
• Fernschild Daniel
• Hilschmann Jessica
• Kali Gergely
• Wenz Gerhard

Classifications

• C08J2353/02

  of vinyl aromatic monomers and conjugated dienes · CPC title

• C08J3/075

  Macromolecular gels · CPC title

• C08G83/007 Primary

  Polyrotaxanes; Polycatenanes · CPC title

• C08J3/246

  Intercrosslinking of at least two polymers · CPC title

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title