Nickel-catalyzed copolymerization of ethylene

Claim 1

Copolymerization process comprising contacting and reacting ethylene, in an oxygen-free atmosphere, at a temperature in the range of about 0° C. to about 200° C., in the presence of a selected nickel-containing catalyst, with one or more 1-olefins of the formula CH 2 ═CHX wherein: X is --R, --OR, --R H R F , --OR F , --Si(OR 1 ) 3-x (R 1 ) x , --OSi(OR 1 ) 3-x (R 1 ) x , --N(R')(R 2 )--Sn(R 1 ) 3 and --B(R 1 ) 2 ; R is hydrocarbyl, provided, however: (i) conjugated aliphatic unsaturation and terminal --C.tbd.CH groups are excluded, and any unsaturation is separated from the enyl group CH 2 ═CH-- by at least one carbon atom; and (ii) any functional substituent selected from --OH, --CO 2 R 2 , --CO 2 Si(OR 1 ) 3-x (R 1 ) x ,--C(O)N(R 1 ) 2 , --N(CH 3 ) 2 , --SOR 2 , --SO 2 R 2 or --OSO 2 R 2 is separated from the enyl group CH 2 ═CH by at least two carbon atoms; R H is C 1-20 hydrocarbylene; R F is C 1-20 perfluorocarbyl, optionally containing in-chain ether oxygen; R' is C 2-10 hydrocarbyl; x is 0 or an integer of 1 to 3; each R 1 , independently, is H or C 1-20 hydrocarbyl; and R 2 is C 1-20 hydrocarbyl, the nickel-containing catalyst selected from: 1(a) The dinickel compound of the formula ##STR37## wherein: R 3 and each R 4 , independently, is H or C 1-20 hydrocarbyl; X 1 is O or S; E 1 is P, As or Sb; and each of R 5 and R 6 , independently, is H, C 1-20 hydrocarbyl or a functional group selected from --13 OR 2 , --Cl, --CO 2 R 2 , --CO 2 M, --C(O)N(R 1 ) 2 , --C(O)R 2 , --SR 2 , --SO 2 R 2 , --OSO 2 R 2 , --SOR 2 , --P(O)(OR 2 ) 2-y (R 1 ) y , --CN, --NHR 2 , --N(R 2 ) 2 , ##STR38## --SI(OR 1 ) 3-x (R 1 ) x , --OSi(OR 1 ) 3-x (R 1 ) x , --NO 2 , --SO 3 M, --PO 3 M 2 and --P(O)(OR 2 ) 2 M wherein M is alkali or alkaline earth metal, ammonium, quaternary ammonium, phosphonium or arsonium, y is 0, 1 or 2 and R 1 , each R 2 , independently, and x are as defined above, or R 5 and R 6 , taken together, is a substituted or unsubstituted C 5-8 alicyclic, C 5-8 heterocyclic or C 6-14 aromatic ring, the heteroatom of the heterocyclic ring being selected from O, N and S; 1(b) the nickel compound of the formula ##STR39## wherein: R 3 , R 4 , R 5 , R 6 , X 1 and E 1 are defined as above and L 1 is a weakly coordinating ligand, or R 3 and L 1 taken together is ##STR40## wherein R" is H, C 1-20 hydrocarbyl or oxyhydrocarbyl or N(R 2 ) 2 wherein R 2 is defined as above: 1(c) the nickel-containing compound of the formula ##STR41## wherein: R 1 , R 4 , R 5 , R 6 , X 1 and E 1 are defined as above; and each R 7 , independently, is H, --OSi(R"') 3 , C 1-20 alkyl or oxyalkyl, C 6-20 aryl, alkaryl, aralkyl or oxyaryl, N(R 2 ) 2 wherein R 2 is as defined above, or halogen, or both R 7 groups, taken together, is a 5 to 8-membered heterocyclic ring wherein the heteroatom is selected from O, N and S; and each R"', independently, is C 1-20 alkyl or oxyalkyl, C 6-20 , alkaryl, aralkyl or oxyaryl; (2) the mixture comprising: (i) the nickel compound of the formula ##STR42## wherein: R 3 , R 4 , R 5 , R 6 , X 1 and E 1 are defined as above and L 2 is a strongly coordinating ligand; and (ii) an acceptor compound which can react irreversibly with L 2 ; (3) the mixture comprising: (i) the nickel compound of the formula ##STR43## wherein: R 4 , R 5 , R 6 , X 1 and E 1 are defined as above; and (ii) a suitable alkylating or arylating compound; and (4) the mixture and comprising: (i) one or more zero-valent olefin-nickel compounds or π-allyl nickel compounds, or a nickel(I) or nickel(II) compound capable of forming said compounds in the presence of a reducing agent; and (ii) the phosphorane of the formula (R 4 ) 3 P═C(R 5 )C(O)R 6 wherein: R 4 , R 5 and R 6 defined as above, with the proviso that at least one R 4 is aryl or substituted aryl.