Living and block copolymerization of ethylene and α-olefins using palladium(II)-α-diimine catalysts

被引:214
作者
Gottfried, AC [1 ]
Brookhart, M [1 ]
机构
[1] Univ N Carolina, Dept Chem, Chapel Hill, NC 27599 USA
关键词
D O I
10.1021/ma025902u
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Living polymerizations of ethylene with palladium(II) diimine complexes coupled with use of a functionalized initiator and/or cleavage of the palladium-polymer bond with various reagents provides a protocol for synthesis of mono- and di-end-functionalized, branched, amorphous polyethylenes. The functional initiator used is the chelate complex [(ArN=C(Me)-C(Me)=NAr)Pd)(CH2)(3)C(O)OMe] [(BAr'(4))] (Ar = 2,6-(iPr)(2)C6H3) (3). The alkyl chain is cleaved by insertion of alkyl acrylates or methyl vinyl ketone, followed by cleavage with Et3SiH to generate alkyl ester or methyl ketone end groups, respectively. Insertion of 5-hexen-1-ol, followed by chain running and beta-elimination, results in formation of aldehyde end groups. Conditions for living polymerization of propylene, 1-hexene, and 1-octadecene have also been established. Rates of first monomer insertion and subsequent chain growth are shown to be a sensitive function of the palladium complex used for initiation and the nature and concentration of auxiliary nitrile ligands. Block copolymers of ethylene and 1-octadecene were prepared under living conditions. The copolymer microstructure differed depending on the order of introduction of the blocks.
引用
收藏
页码:3085 / 3100
页数:16
相关论文
共 74 条
[1]   NMR detection of living intermediates prepared from activated [NON]ZrMe2 ([NON]2- = [(t-Bu-d6-N-o-C6H4)2O]2-) and olefins [J].
Baumann, R ;
Schrock, RR .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1998, 557 (01) :69-75
[2]   Synthesis of titanium and zirconium complexes that contain the tridentate diamido ligand, [((t-Bu-d(6))N-o-C6H4)(2)O](2-)([NON](2-)) and the living polymerization of 1-hexene by activated [NON]ZrMe2 [J].
Baumann, R ;
Davis, WM ;
Schrock, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (16) :3830-3831
[3]   COBALT(III)-CATALYZED LIVING POLYMERIZATION OF ETHYLENE - ROUTES TO END-CAPPED POLYETHYLENE WITH A NARROW MOLAR-MASS DISTRIBUTION [J].
BROOKHART, M ;
DESIMONE, JM ;
GRANT, BE ;
TANNER, MJ .
MACROMOLECULES, 1995, 28 (15) :5378-5380
[4]   DETECTION OF AN ALKYL ETHYLENE COMPLEX DURING ETHYLENE POLYMERIZATION BY A CO(III) CATALYST - ENERGETICS OF THE BETA-MIGRATORY INSERTION REACTION [J].
BROOKHART, M ;
VOLPE, AF ;
LINCOLN, DM ;
HORVATH, IT ;
MILLAR, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (14) :5634-5636
[5]  
Brookhart M, 1991, POLYM PREPR, V32, P461
[6]   Metallocene-mediated olefin polymerization with B-H chain transfer agents: Synthesis of chain-end functionalized polyolefins and diblock copolymers [J].
Chung, TC ;
Xu, G ;
Lu, YY ;
Hu, YL .
MACROMOLECULES, 2001, 34 (23) :8040-8050
[7]  
Coates GW, 2002, ANGEW CHEM INT EDIT, V41, P2236, DOI 10.1002/1521-3773(20020703)41:13<2236::AID-ANIE2236>3.0.CO
[8]  
2-3
[9]   Novel branching topology in polyethylenes as revealed by light scattering and 13C NMR [J].
Cotts, PM ;
Guan, ZB ;
McCord, E ;
McLain, S .
MACROMOLECULES, 2000, 33 (19) :6945-6952
[10]  
DOI Y, 1987, MAKROMOL CHEM, V188, P1273