Process for preparing olefin-acrylate block copolymers by ATRP

A process for preparing an olefin-acrylate block copolymer, the process comprising:

• a) Performing atom transfer radical polymerization (ATRP), by combining ATRP material comprising an acrylate monomer with the formula (III), an initiator having a radically transferrable atom or group, a transition metal compound, and a ligand, thereby forming a macroinitiator;
• and
• b) combining reaction materials comprising an alpha-substituted acrylate and the macroinitiator, thereby forming the olefin-acrylate block copolymer wherein:
• the alpha-substituted acrylate has the formula (II)
• wherein R is a polyolefinyl group and R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
• the acrylate monomer has the formula (III):
• wherein R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
• each R2 independently is hydrogen or a methyl group;
• the initiator has the formula (IV):
• the macroinitiator has the formula (V):
• polyacrylate-(X)y (V);
• the olefin-acrylate block copolymer has the formula (VI):
• wherein:
• each R1 independently is hydrogen or a C1-C30 hydrocarbyl group;
• each R2 independently is hydrogen or a methyl group;
• each R independently is a polyolefinyl group;
• m is from 1 to 50;
• each y independently is from 1 to 100;
• each X independently is selected from the group consisting of a halide, OR10, SR14, SeR14, —SCN (thiocyanate), OC(═O)R14, OP(═O)R14, OP(═O)(OR14)2, OP(═O)OR14, O—N(R14)2, and S—C(═S)N(R14)2, where R14 is aryl or a straight or branched C1-C20 alkyl group, or when an N(R14)2 group is present, the two R14 groups may be joined to form a 5-, 6-, or 7-membered heterocyclic ring, and where R10 is alkyl of from 1 to 20 carbon atoms, in which each of the hydrogen atoms may be independently replaced by halide;
• R11, R12, and R13 are each independently selected from the group consisting of H, halide, C1-C20 alkyl, C3-C8 cycloalkyl, C(═Y)R5, C(═Y)NR6R7, COCl, OH, CN, C2-C20 alkenyl or alkynyl, oxiranyl, glycidyl, aryl, heterocyclyl, aralkyl, aralkylene (aryl-substituted alkenyl, and alkenyl is vinyl which may be substituted with one or two C1-C6 alkyl groups and/or halogen atoms), C1-C6 alkyl in which from 1 to all of the hydrogen atoms are replaced with halogen and C1-C6 alkyl substituted with from 1 to 3 substituents selected from the group consisting of C1-C4 alkoxy, aryl, heterocyclyl, C(═Y)R6, C(═Y)NR6R7, oxiranyl and glycidyl;
• such that no more than two of R11, R12 and R13 are H;
• Y may be NR8 or O;
• R5 is alkyl of from 1 to 20 carbon atoms, alkoxy of from 1 to 20 carbon atoms, aryloxy or heterocyclyloxy, R6 and R7 are independently H or alkyl of from 1 to 20 carbon atoms, or R6 and R7 may be joined together to form an alkylene group of from 2 to 5 carbon atoms, thus forming a 3- to 6-membered ring, and R8 is H, straight or branched C1-C20 alkyl and aryl;
• and
• “polyacrylate” represents the polyacrylate resulting from ATRP of the acrylate monomer.