Oxetane polymers and methods of preparation thereof

A process for preparation of an oxetane polymer, the process comprising photopolymerizing an epoxide accelerant with one or more equivalents of a 3,3-disubstituted oxetane, wherein the oxetane polymer is a compound of formula (Ia):

• wherein
• R1 is H, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, or heteroalkynyl;
• wherein R1 is optionally substituted with one or more of halogen, hydroxy, oxo, epoxy, R7, or combinations thereof;
• R2 is H, alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, or heteroalkynyl;
• wherein R2 is optionally substituted with one or more of halogen, hydroxy, oxo, epoxy, R8, or combinations thereof;
• wherein R1 and R2 cannot both be H;
• or R1 and R2 jointly form R9;
• R3 is alkyl, alkenyl, alkynyl, carbocycle or heterocycle;
• wherein R3 is optionally substituted with halogen, hydroxy, oxo, epoxy, carbocycle, heterocycle, or combinations thereof;
• R4 is alkyl, alkenyl, alkynyl, carbocycle or heterocycle;
• wherein R4 is optionally substituted with halogen, hydroxy, oxo, epoxy, carbocycle, heterocycle, or combinations thereof;
• R5 is alkyl, alkenyl, alkynyl, carbocycle or heterocycle;
• wherein R5 is optionally substituted with halogen, hydroxy, oxo, epoxy, carbocycle, heterocycle, or combinations thereof;
• R6 is H;
• or R3 and R4 jointly form R10;
• wherein R3, R4, R5, and R6 cannot all be H at the same time;
• wherein any three of R3, R4, R5, and R6 cannot be H at the same time;
• wherein both R3 and R5 cannot be H at the same time;
• R7 is carbocycle or heterocycle;
• wherein R7 is optionally substituted with alkyl, alkenyl, alkynyl, halogen, hydroxy, hydroxy alkyl, oxo, epoxy, epoxy alkyl, or combinations thereof;
• R8 is carbocycle or heterocycle;
• wherein R8 is optionally substituted with alkyl, alkenyl, alkynyl, halogen, hydroxy, hydroxy alkyl, oxo, epoxy, epoxy alkyl, or combinations thereof;
• R9 is carbocycle or heterocycle;
• wherein R9 is optionally substituted with alkyl, alkenyl, alkynyl, halogen, hydroxy, hydroxy alkyl, oxo, epoxy, epoxy alkyl, or combinations thereof;
• R10 is carbocycle or heterocycle;
• wherein R10 is optionally substituted with alkyl, alkenyl, alkynyl, halogen, hydroxy, hydroxy alkyl, oxo, epoxy, epoxy alkyl, or combinations thereof;
• R49 is H or alkyl;
• and
• n is an integer from 1 to 50;
• the epoxide accelerant is a compound of formula (IIa):
• wherein R3, R4, R5, and R6 are as defined above;
• and the 3,3-disubstituted oxetane is a compound of formula (IIIa):
• wherein R1 and R2 are as defined above.