用于异戊二烯聚合的新型高效单中心稀土（RE）催化剂体系
Novel High-Efficiency Single-Site Rare Earth (RE) Catalyst System for Isoprene Polymerization.
作者信息
Kang Di, Ma Rongqing, Hu Hongfan, Zhou Yi, Mao Guoliang, Xin Shixuan
机构信息
Provincial Key Laboratory of Polyolefin New Materials, College of Chemical Engineering, Northeast Petroleum University, Daqing 163318, China.
PetroChina Shanghai Advanced Materials Research Institute Co., Ltd., 1 Shengang Avenue, Lingang District, Shanghai 201306, China.
出版信息
Polymers (Basel). 2025 Apr 29;17(9):1219. doi: 10.3390/polym17091219.
Bis-(-dipheylphosphinophenyl)amine, a tridentate (PNP) chelating ligand, and several of their Rare Earth (RE) metal complexes, [bis-(-dipheylphosphinophenyl)amido]-RER, {[(CH)P--(CH)]NMR (R = -CH--(CH)NMe: M = Y, ; Nd, ; Gd, ;), are prepared in high yields. When activated with the strong Lewis acid MMAO-7, all these complexes exhibit catalytic activity toward the polymerization of isoprene (IP) in non-protic hydrocarbons. While the Nd complex () showed moderate activity and stereoselectivity, the Y and Gd complexes ( and ) exhibited extremely high catalytic efficiency in IP homo-polymerization, and produced polyisoprene rubber (PI) with 95% to over 99% -1,4 stereoselectivity and narrow polydispersity indices (<2.0). Moreover, under industrially relevant conditions, complex can catalyze IP to produce ultrahigh molecular weight PI (UHMW-PI, MW up to 1200-2600 kg/mol) rubber with a very narrow polydispersity index (PDI ca. 1.1-1.6), a high-performance elastomeric material mimic of natural rubber (NR).
双（-二苯基膦基苯基）胺，一种三齿（PNP）螯合配体，及其几种稀土（RE）金属配合物，[双（-二苯基膦基苯基）酰胺基]-RER，{[（CH）P--（CH）]NMR（R = -CH--（CH）NMe：M = Y，；Nd，；Gd，；），以高产率制备。当用强路易斯酸MMAO-7活化时，所有这些配合物对非质子烃中的异戊二烯（IP）聚合均表现出催化活性。虽然钕配合物（）显示出中等活性和立体选择性，但钇和钆配合物（和）在IP均聚中表现出极高的催化效率，并生成具有95%至超过99%的-1,4立体选择性和窄多分散指数（<2.0）的聚异戊二烯橡胶（PI）。此外，在工业相关条件下，配合物可以催化IP生成超高分子量PI（UHMW-PI，MW高达1200-2600 kg/mol）橡胶，其多分散指数非常窄（PDI约为1.1-1.6），是一种模仿天然橡胶（NR）的高性能弹性体材料。
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