Multifunctional nitroxide-mediated polymerization initiators and multi-armed polymers and hydrogels formed therefrom

Patent metadata

Field	Value
Publication number	US-2021061957-A1
Application number	US-202016999822-A
Country	US
Kind code	A1
Filing date	Aug 21, 2020
Priority date	Aug 28, 2019
Publication date	Mar 4, 2021
Grant date	—

Abstract

In some aspects, the present disclosure pertains to multi-arm polymers that comprise a core and a plurality of polymer segments having a first end that is covalently attached to the core and (a) a second end comprising a moiety that comprises a reactive end group, wherein the polymer segments comprise one or more hydrophilic aprotic NMP-polymerizable monomers, and wherein the reactive multi-arm polymer comprises nitroxide radicals or (b) a second end comprising a moiety that comprises an alkoxyamine group, wherein the core is a polyol residue, and wherein the polymer segments comprise one or more NMP-polymerizable monomers. In some aspects, the present disclosure pertains to a multifunctional alkoxyamine molecule comprising a core and a plurality of alkoxyamine groups covalently attached to the core, wherein the core is a polyol residue.

First claim

1 . A multi-arm polymer comprising a core and a plurality of polymer segments having a first end that is covalently attached to the core and a second end comprising a moiety that comprises a reactive group, wherein the polymer segments comprise one or more hydrophilic aprotic NMP-polymerizable monomers, and wherein the multi-arm polymer comprises nitroxide radicals.

2 . The multi-arm polymer of claim 1 , wherein the core is selected from a polyol residue and a silsesquioxane core.

3 . The multi-arm polymer of claim 1 , wherein the reactive group is an electrophile or a nucleophile.

4 . The multi-arm polymer of claim 1 , wherein the moiety that comprises a reactive group further comprises a hydrolysable ester group.

5 . A system comprising (a) a first composition comprising a multi-arm polymer in accordance with claim 1 and (b) a second composition comprising a multifunctional compound that comprises functional groups that are reactive with the reactive groups of the multi-arm polymer.

6 . The system of claim 5 , further comprising a delivery device.

7 . A crosslinked reaction product of (a) a multi-arm polymer in accordance with claim 1 and (b) a multifunctional compound that comprises functional groups that are reactive with the reactive groups of the multi-arm polymer.

8 . A multi-arm polymer comprising a core and a plurality of polymer segments having a first end that is covalently attached to the core and a second end comprising a moiety that comprises an alkoxyamine group, wherein the core is a polyol residue and wherein the polymer segments comprise one or more NMP-polymerizable monomers.

9 . The multi-arm polymer of claim 8 , wherein the polymer segments comprise one or more NMP-polymerizable hydrophilic aprotic monomers.

10 . The multi-arm polymer of claim 8 , wherein the polymer segments comprise N-vinyl pyrrolidone monomers.

11 . The multi-arm polymer of claim 8 , wherein the polyol residue is a residue of a polyol selected from straight-chained, branched and cyclic aliphatic polyols, straight-chained, branched and cyclic polyhydroxy ethers, straight-chained, branched and cyclic polyhydroxy polyethers, straight-chained, branched and cyclic polyhydroxyalkyl ethers, and straight-chained, branched and cyclic polyhydroxyalkyl polyethers.

12 . The multi-arm polymer of claim 8 , wherein the alkoxyamine group comprises four alkyl groups attached to two carbons atoms in a-positions relative to the alkoxyamine group nitrogen atom.

13 . A multifunctional alkoxyamine molecule comprising a core and a plurality of alkoxyamine groups covalently attached to the core, wherein the core is a polyol residue.

14 . The multifunctional alkoxyamine molecule of claim 13 , wherein the polyol residue is a residue of a polyol selected from straight-chained, branched and cyclic aliphatic polyols, straight-chained, branched and cyclic polyhydroxy ethers, straight-chained, branched and cyclic polyhydroxy polyethers, straight-chained, branched and cyclic polyhydroxyalkyl ethers, and straight-chained, branched and cyclic polyhydroxyalkyl polyethers.

15 . The multifunctional alkoxyamine molecule of claim 13 , wherein the polyol residue is a residue of a polyol selected from sugars, sugar alcohols, sugar oligomers, sugar alcohol oligomers, sugar polymers, and sugar alcohol polymers.

16 . The multifunctional alkoxyamine molecule of claim 13 , wherein the polyol residue is an ether or polyether.

17 . The multifunctional alkoxyamine molecule of claim 13 , wherein the plurality of alkoxyamine groups is covalently attached to the core via an ester linkage.

18 . The multifunctional alkoxyamine molecule of claim 13 , wherein the plurality of alkoxyamine groups comprise four alkyl groups attached to two carbons atoms in α-positions relative to the alkoxyamine group nitrogen atom.

19 . The multifunctional alkoxyamine molecule of claim 13 , wherein the plurality of alkoxyamine groups are cyclic or acyclic alkoxyamine groups.

20 . A method of forming a multifunctional alkoxyamine molecule in accordance with claim 13 , comprising (a) reacting hydroxyl groups of a polyol with an α-halogenated-C 2 -C 6 acid halide to form an intermediate compound, followed by reaction of the intermediate compound with a nitroxide radical in a nitroxide radical coupling step to form a multifunctional alkoxyamine molecule.

Assignees

• Boston Scient Scimed Inc

Inventors

• Delaney Jr Joseph T
• Grosso Paul V
• Kummailil John
• Dyndikova Tatyana
• Rehder Carey

Classifications

• C08F2438/02

  Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO] · CPC title

• C08F283/12 Primary

  on to polysiloxanes · CPC title

• C07F9/6596

  having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms · CPC title

• C07F7/21

  Cyclic compounds having at least one ring containing silicon, but no carbon in the ring · CPC title

• A61L27/58

  Materials at least partially resorbable by the body · CPC title