ISSN:
0887-624X
Keywords:
neodymium tricarboxylate
;
cis-poly (2,3-dimethylbutadiene)
;
copolymerization of dienes
;
cis-1,4 polymerization mechanism
;
back-biting coordination
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
It was found that poly(butadiene), poly(isoprene), and poly(2,3-dimethylbutadiene) with high cis-1,4 content were obtained with Nd(OCOR)3-(i-Bu)3Al-Et2AlCl catalysts (R = CF3, CCl3, CHCl2, CH2Cl, CH3) in hexane at 50°C [cis-1,4 content: poly(BD), 〉 98%; poly(IP), ≥ 96%; poly(DMBD), ≥ 94%]. Copolymerization of IP and styrene (St) was carried out at various monomer feed ratios to evaluate the monomer reactivity ratio and cis-1,4 content of the diene unit and then to elucidate the cis-1,4 polymerization mechanism of IP. The cis-1,4 content of the IP unit in the copolymers decreased with increasing St content in the copolymers. The cis-1,4 polymerization was disturbed by incorporating St unit in the copolymers, since the penultimate St unit hardly coordinates to the neodymium metal, resulting in a decrease of the cis-1,4 content in the copolymers. That is, the cis-1,4 polymerization of IP is suggested to be controlled by a back-biting coordination of the penultimate diene unit. On the other hand, in the case of poly(BD-co-IP) and poly(BD-co-DMBD), the cis-1,4 content of the BD, IP, and DMBD units in the copolymers was almost constant (cis: 94-98%), irrespective of the monomer feed ratios and polymerization temperature. Consequently, the penultimate IP and DMBD units favorably control the terminal BD, IP, or DMBD unit to the cis-1,4 configuration through the back-biting coordination. For the monomer reactivity ratios, a clear difference was observed in each system: rBD = 1.22, rIP = 1.14; rBD = 40.9, rDMBD = 0.15. Low polymerizability of DMBD was mainly ascribed to the steric effect of the methyl substituents. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1707-1716, 1998
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
