METHOD OF PRODUCING MACROCYCLIC POLYMERS

• US 20130131275A1
• Filed: 05/05/2011
• Published: 05/23/2013
• Est. Priority Date: 05/05/2010
• Status: Active Grant

• Current Assignee: Bucknell University
• Original Assignee: Bucknell University
• Inventors: Tillman, Eric S., Voter, Andrew F.
• Granted Patent: US 9,012,597 B2
• Time in Patent Office: Days
• US Class Current: 525/242
• CPC Class Codes: C08F 112/08 Styrene
• CPC Class Codes: C08F 2438/01 Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 8/48 Isomerisation; Cyclisation

Abstract

A method for producing a macrocyclic polymer comprising: (a) polymerizing a monomer using a dibrominated initiator having either an aromatic or ester moiety via atom transfer radical polymerization (ATRP) to form a polymer precursor having brominated, phenylated end groups; and (b) cyclizing the polymer precursor using intramolecular atom transfer radical coupling (ATRC) to form the macrocyclic polymer.

Claims

1. A method for producing a macrocyclic polymer comprising:

(a) polymerizing a monomer using a dibrominated initiator having either an aromatic or ester moiety via atom transfer radical polymerization (ATRP) to form a polymer precursor having brominated, phenylated end groups; and

(b) cyclizing said polymer precursor using intramolecular atom transfer radical coupling (ATRC) to form said macrocyclic polymer.

2. The method of claim 1, wherein step (a) comprises:

(i) polymerizing said monomer to form an intermediate polymer with brominated end groups; and

(ii) block polymerizing said intermediate polymer to add terminal block polymers having phenylated end groups to form said polymer precursor.

3. The method of claim 1, wherein said initiator has the following structure:

4. The method of claim 3, wherein said aryl group is selected from phenyl, napthyl, flourenyl, anthracenyl groups.

5. The method of claim 4, wherein said aryl group is phenyl.

6. The method of claim 5, wherein said initiator is benzal bromide.

7. The method of claim 3, wherein said ester group comprises:

RCO₂R′

, wherein R and R′

are selected independently form substituted and non-substituted alkyls, alkylenes, alkenyls, alkenylenes, alkynyls, alkoxys, aryls, aralkyls, and hydrocarbyls.

8. The method of claim 7, wherein R and R′

are independently selected from substituted and non-substituted methyls, ethyls, propryls, and butyls.

9. The method of claim 8, wherein said initiator is ethylene bis(2-bromoisobutyrate).

10. The method of claim 3, wherein said precursor polymer has the following structure:

11. The method of claim 10, wherein R2 is phenyl.

12. The method of claim 3, wherein said precursor polymer has the following structure:

13. The method of claim 12, wherein each instance of R2 is selected independently from substituted and non-substituted aryls and acrylates.

14. The method of claim 13, wherein said R2 is an acrylate.

15. The method of claim 14, wherein said R2 is methacrylate,

16. The method of claim 1, wherein said monomer is at least one of the following monomers:

styrene, oxybenzylmethylenglycolanhydride, chloroprene, amides, vinyl chloride, ethylene, propylene, acrylonitrile, vinyl butyral, tetrafluoroethylene, methyl methacrylate, carbonate, siloxane, and phosphazene.

17. The method of claim 16, wherein said precursor polymer has brominated, phenylated end groups and comprises at least one of:

polystyrene, synthetic rubber, polyoxybenzylmethylenglycolanhydride, polychloroprene, polyamides, polystyrene, polyvinyl chloride, polyethylene, polypropylene (low and high density), polyacrylonitrile, polyvinyl butyral, polytetrafluoroethylene, poly(methyl methacrylate), polycarbonates, polysiloxane, and polyphosphazene.

18. The method of claim 1, wherein said ATRC comprises a step in which said end groups are radicalized by cleaving a moiety from therefrom.

19. The method of claim 18, wherein said step comprises a metal-catalyzed, hemolytic cleavage.

20. The method of claim 1, wherein said macrocyclic polymer is cyclic polystyrene.