Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform

A method of making a multifunctional methylene malonate monomer comprising:

• (a) reacting at least one methylene malonate monomer with a diol, a polyol or a polymeric resin having at least two hydroxyl groups in the presence of an enzymatic catalyst to form a reaction complex wherein the at least one methylene malonate monomer is provided in an excess amount with respect to the diol, polyol or polymeric resin having at least two hydroxyl groups;
• and
• (b) recovering multifunctional methylene malonate monomer comprising more than one methylene malonate core formula linked by the diol, polyol or polymeric resin having at least two hydroxyl groups from the reaction complex;
• (c) adding a stabilizer to the reaction complex formed in step (a);
• wherein in step (a) the at least one methylene malonate monomer is provided in an excess amount with respect to the diol, polyol or polymeric resin having at least two hydroxyl groups,
• recovering multifunctional methylene malonate monomer in step (b) includes separating the multifunctional methylene malonate monomer from the excess methylene malonate monomer and the diol, polyol or polymeric resin having at least two hydroxyl groups;
• and the diol, polyol or polymeric resin having at least two hydroxyl groups correspond to the formula (HO)-[A]-(OH)m wherein:
• [A] is independently selected from —(CRARB)n—, —(CRARB)n—O(C═O)—(CH2)1-15—(C═O)O—(CRARB)n—, —(CH2)n—[CY]—(CH2)n, a polybutadienyl linking group, a polyethylene glycol linking group, a polyether linking group, a polyurethane linking group, an epoxy linking group, a polyacrylic linking group, or a polycarbonate linking group;
• each instance of RA or RB is independently selected from H, C1-C15 alkyl, a moiety corresponding to the formula:
• wherein:
• L is a linking group selected from the group consisting of alkylene, haloalkylene, cycloalkylene, cycloalkylene, or alkoxy-(alkylene), each of which may be optionally branched and each of which may be optionally substituted by alkyl, haloalkyl, C1-C15 alkoxy, each of which may be optionally branched;
• R3 is independently selected from C1-C15 alkyl, C2-C15 alkenyl, halo-(C1-C15 alkyl), C3-C6 cycloalkyl, halo-(C3-C6 cycloalkyl), or alkoxy —(C1-15 alkyl), each of which may be optionally substituted by C1-C15 alkyl, halo-(C1-C15 alkyl), and
• CY is independently selected from an alkyl, alkenyl, haloalkyl, cycloalkyl, halo cycloalkyl, or alkoxy -(alkyl) group;
• and
• each instance of m and n are independently an integer from 1 to 25.