Crystallization-driven self-strengthening polymers and associated compositions and methods

A method of forming a functionalized crosslinked acrylate copolymer, comprising:

• partially copolymerizing a monomer mixture comprising
• a first monomer selected from the group consisting of C10-C24-alkyl (meth)acrylates, C10-C24-alkenyl (meth)acrylates, C10-C24-alkyl (meth)acrylamides, C10-C24-alkenyl (meth)acrylamides, and combinations thereof;
• a second monomer selected from the group consisting of (meth)acrylic acid, C1-C8-alkyl (meth)acrylates, C1-C8-alkyl (meth)acrylamides, 2-carboxyethyl (meth)acrylate, C2-C8-hydroxyalkyl (meth)acrylates, C2-C8-hydroxyalkyl (meth)acrylamides, ethylene glycol methyl ether (meth)acrylate, ethylene glycol methyl ether (meth)acrylamide, mono-2-(methacryloyloxy)ethyl maleate, mono-2-(methacryloyloxy)ethyl succinate, itaconic acid,
• wherein X is hydrogen or methyl, and n is 2, 3, 4, 5, 6, 7, 8, 9, or 10, and combinations thereof;
• and
• a third monomer selected from the group consisting of C1-C6-alkylene bis((meth)acrylate)s, C1-C6-alkylene bis((meth)acrylamide)s, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, diurethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, polycaprolactone di(meth)acrylate, polycaprolactone tri(meth)acrylate, and combinations thereof
• to form a functionalized crosslinked acrylate copolymer comprising
• 15 to 63 mole percent of first units derived from the first monomer,
• 35 to 83 mole percent of second units derived from the second monomer, and
• 2 to 50 mole percent of third units derived from the third monomer;
• wherein of the 2 to 50 mole percent of third units derived from the third monomer, 0.6 to 25 mole percent have at least one pendant (meth)acryloyloxy or (meth)acrylamido group, and 25 to 49.4 mole percent have zero pendant (meth)acryloyloxy or (meth)acrylamido groups;
• and
• wherein all mole percent values are based on total moles of first units, second units, and third units in the functionalized crosslinked acrylate copolymer.

A curable composition comprising:

• an unfunctionalized uncrosslinked acrylate block copolymer comprising a first block and a second block;
• wherein
• the first block comprises first units derived from a first monomer selected from the group consisting of C10-C24-alkyl (meth)acrylates, C10-C24-alkenyl (meth)acrylates, C10-C24-alkyl (meth)acrylamides, C10-C24-alkenyl (meth)acrylamides, and combinations thereof;
• and
• the second block comprises second units is derived from a second monomer selected from the group consisting of (meth)acrylic acid, C1-C8-alkyl (meth)acrylates, C1-C8-alkyl (meth)acrylamides, 2-carboxyethyl (meth)acrylate, C2-C8-hydroxyalkyl (meth)acrylates, C2-C8-hydroxyalkyl (meth)acrylamides, ethylene glycol methyl ether (meth)acrylate, ethylene glycol methyl ether (meth)acrylamide, mono-2-(methacryloyloxy)ethyl maleate, mono-2-(methacryloyloxy)ethyl succinate, itaconic acid,
• wherein X is hydrogen or methyl, and n is 2, 3, 4, 5, 6, 7, 8, 9, or 10, and combinations thereof;
• wherein the unfunctionalized uncrosslinked acrylate block copolymer comprises 15 to 65 mole percent of first units and 35 to 85 mole percent of second units, based on the total mole percent of first units and second units in the unfunctionalized uncrosslinked acrylate block copolymer;
• and
• a polymerizable monomer comprising a sixth monomer comprising two or more reactive groups selected from the group consisting of (meth)acryloyloxy groups, (meth)acrylamido groups, and combinations thereof.