Production of meta-block copolymers by polymer segment interchange

A process for preparing a product mixture comprising meta-block copolymers by contacting a metathesis catalyst under metathesis conditions with a composition comprising two or more ethylenically unsaturated polymers, each polymer having a molecular weight of at least 1000 g/mole, said unsaturation defining one or more polymer blocks in each ethylenically unsaturated polymer, at least one polymer block in the ethylenically unsaturated polymers comprising internal unsaturation and being chemically distinguishable from at least one polymer block in at least one other ethylenically unsaturated polymer, wherein the ethylenic content of each of the two or more ethylenically unsaturated polymers is from 0.1 to 3 mole percent and distribution of the ethylenic content in the ethylenically unsaturated polymers is substantially random such that at least 99 percent of multiple unsaturations in the ethylenically unsaturated polymers are separated by at least 6 methylene or substituted methylene units, characterized in that each meta-block copolymer in the product mixture comprises a random distribution of said chemically distinguishable polymer blocks;

• wherein at least two of the chemically distinguishable blocks possess a difference in expected Tg of at least 40° C.;
• wherein at least two of the chemically distinguishable blocks have an expected solubility parameter difference of at least 1.0;
• and wherein the combination of the chemically distinguishable polymer blocks is a one of the following combinations (a) to (i):
• (a) a partially hydrogenated polybutadiene and a partially hydrogenated butadiene nitrile rubber;
• (b) an unsaturated polyurethane and a polyethylene-co-butadiene);
• c) an unsaturated polycarbonate and one of polyethylene-co-butadiene) and poly(ethylene-co-octene-co-butadiene);
• d) an unsaturated polycarbonate and a block selected from the group consisting of an unsaturated polysiloxane, a fluoropolymer, a chlorinated polyolefin, a polytetrahydrofuran and EPDM;
• (e) a poly(ethylene oxide) and a polyethylene-co-butadiene);
• (f) a poly(ethylene-co-butadiene) and a poly(ethylene-co-octene-co-butadiene);
• (g) an unsaturated polyester and a poly(ethylene-co-butadiene);
• (h) a poly(styrene-co-butadiene-styrene) and poly(ethylene-co-butadiene);
• and
• (i) an unsaturated polycarbonate, a poly(styrene-co-butadiene-co-styrene), and a third polymer block comprising poly(ethylene-co-butadiene);
• and wherein
• the catalyst is of the formula:
• wherein:
• MA is ruthenium or osmium;
• XA and XB are the same or different anionic ligand;
• LA is a neutral electron donor ligand;
• LB is a neutral electron donor ligand or a nitrogen containing heterocyclic carbene;
• and
• RA and RB are independently each occurrence hydrogen, or an alkyl, alkenyl, alkenyl, aryl, carboxylate, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkylsulfonyl, alkylsulfinyl, or silyl group of up to 20 atoms not counting hydrogen, an alkyl, alkoxy, aryl, aralkyl, haloalkyl, haloalkoxy, haloaryl or haloalkaryl substituted derivative thereof;
• or a functionalized derivative of any of the foregoing wherein the functional group is hydroxyl, thiol, alcohol, sulfonic acid, phosphine, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, imide, imido, nitro, carboxylic acid, disulfide, carbonate, isocyanate. carbodiimide, carboalkoxy, carbamate, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, oxime, hydrazide, enamine, sulfone, sulfide, sulfenyl, or halogen.