Polymers bearing pendant pentafluorophenyl ester groups, and methods of synthesis and functionalization thereof

A method of preparing a cyclic carbonyl monomer, comprising:

• forming a first mixture comprising a precursor compound, bis(pentafluorophenyl) carbonate, an optional solvent, and a catalyst;
• wherein the precursor compound has a structure comprising two or more carbons, a carboxy group, and two X groups, each X group independently selected from the group consisting of hydroxyl group, primary amine, secondary amine, thiol group, and combinations thereof;
• and
• agitating the first mixture at a temperature effective to form a second mixture comprising the cyclic carbonyl monomer;
• wherein the cyclic carbonyl monomer comprises a pentafluorophenyl ester derived from the carboxy group, and a cyclic carbonyl group derived from the two X groups, the cyclic carbonyl group selected from the group consisting of cyclic carbonate, cyclic urea, cyclic carbamate, cyclic thiocarbonate, cyclic thiocarbamate, and cyclic dithiocarbonate.

A method of ring-opening polymerization, comprising:

• forming a reaction mixture comprising a cyclic carbonyl monomer, a catalyst, an initiator, and an optional solvent;
• and
• agitating the reaction mixture with optional heating to form a biodegradable polymer derived from the cyclic carbonyl monomer;
• wherein the cyclic carbonyl monomer is selected from the group consisting of MTC-NiP, MTC-NMe2, MTC-BnAmine, MTC-OCH2CH2CH2Br, MTC-OCH2CHCH2, MTC-dinitroPHS, MTC-TFE, and combinations thereof.

A biodegradable polymer, comprising:

• a chain fragment;
• and
• a first polymer chain;
• wherein i) the chain fragment comprises a first backbone heteroatom, the first backbone heteroatom linked to a first end unit of the first polymer chain, the first backbone heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur, ii) the first polymer chain comprises a second end unit comprising a nucleophilic group selected from the group consisting of hydroxy group, primary amine groups, secondary amine groups, and thiol group, and iii) the first polymer chain comprises a first repeat unit comprising a) a backbone functional group selected from the group consisting of carbonate, ureas, carbamates, thiocarbamates, thiocarbonate, and dithiocarbonate, and b) a tetrahedral backbone carbon, the tetrahedral backbone carbon being linked to a first side chain comprising a pentafluorophenyl ester group.

A method, comprising:

• forming a first mixture comprising a catalyst, an initiator comprising a nucleophilic group selected from the group consisting of alcohols, amines, and thiols, an optional accelerator, an optional solvent, and a first cyclic carbonyl compound comprising a pentafluorophenyl ester group;
• and
• agitating the first mixture, thereby forming a first ROP polymer by ring opening polymerization of the first cyclic carbonyl compound, the first ROP polymer comprising a first polymer chain linked to a chain fragment derived from the initiator;
• wherein i) the chain fragment comprises a first backbone heteroatom derived from the nucleophilic group, the first backbone heteroatom linked to a first end unit of the first polymer chain, the first backbone heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur, ii) the first polymer chain comprises a second end unit comprising a nucleophilic group selected from the group consisting of hydroxy group, primary amine groups, secondary amine groups, and thiol group, and iii) the first polymer chain comprises a first repeat unit, the first repeat unit comprising a) a backbone functional group selected from the group consisting of carbonate, ureas, carbamates, thiocarbamates, thiocarbonate, and dithiocarbonate, and b) a tetrahedral backbone carbon, the tetrahedral backbone carbon being linked to a first side chain comprising a pentafluorophenyl ester group.