聚合物分子设计的原理与方法-5-26.ppt

Fig. 9. Most active lanthanide-based catalysts used for non-stereoselective styrene polymerization Higher activities were observed with Nd and Yb guanidinate complexes (100–101), as expected for complex essupported by bidentate ligand without bulky Cp*. These complexes gave 60–100% yield within 10 min at 70–100?C for [St]/[Ln] = 300–500 (activity ranging from 200 to 900 kg PS/(molLn h)) and polystyrenes with higher molecular weights (Mn = 17200–58900 g/mol, Mw/Mn = 1.4–2.0) but still an atactic microstructure (rr 53%) . One of the highest activity at room temperature for styrene polymerization was reported with polymeric divalent Smderivatives (105–110) [Cp?2 Sm(THF)m(ER)(-Cp?)K(THF)n]x(ER = O-2,6-tBu-4-MeC6H2, O-2,6-iPrC6H3, S-2,4,6-iPrC6H2,HN-2,4,6-iPrC6H2, HP-2,4,6-tBuC6H2, N(SiMe3)2) , yielding atactic materials with high molecular weight (Mn = 82000–350000 g/mol, Mw/Mn = 1.4–2.5) . The activity was dependent on theER ligand: the less sterically demanding O-2,6-iPrC6H3 and the more electron-donating amide gave the best results. More recently, alkyl and silyl analogues (111–116) were also reported to show high activity for styrene polymerization (100% conversion of 700 styrene . at room temperature within 5 min) and like with their parent complexes 105–110, high molecular weight polymers were obtained (Mn = 42000–140000 g/mol, Mw/Mn = 1.2–3.2) . As for other divalent lanthanide species, a one-electron transfer mechanism (Scheme 6) was proposed for those systems. Scheme 6. Proposed styrene polymerization mechanism with divalent Sm species Towards selectivity: Group 3 systems giving syndiotactic-enriched polystyrene Binary or ternary Nd-based systems incorporating Carboxylate Nd(C5H9(CH2)nCOO)3/Al(iBu)3 (117) or phosphate Nd(O(O)P(OCH2CH(Et) (CH2)3CH3))3/MgBu2/HMPA(118) were reported to give syndio-rich polystyrene with moderate activity . Similar results were obtained with some MAO-activated lanthanidoc