Atomistic chemical computation of Olefin polymerization reaction catalyzed by (pyridylamido)hafnium(IV) complex: Application of Red Moon simulation

Abstract

We have realized the microscopic simulation of olefin polymerization, that is, the simulation of the catalytic polymerization (CP) reaction system composed of (pyridylamido)hafnium (IV) complex as the catalyst. For this purpose, we adopted Red Moon (RM) method, a novel molecular simulation method to simulate the complex reaction system. First, according to the previous research, with the help of the QM calculation, we proposed a model system and elementary processes and explained the theoretical treatment of the simulation by the RM method (the RM simulation). In addition, we also proposed a macroscopic simulation based on chemical kinetics simulation. Then, we performed two simulations and compared them in terms of the effective time evolution of the three macroscopic physical quantities, the number-average molecular weight M n , the massaverage molecular weight M w , and the molar-mass dispersity Đ M . The comparison showed that the two simulations are in quantitative or partially qualitative agreement with each other. Therefore, it is concluded that the RM simulation could not only simulate the CP reaction process microscopically, but also it is connected essentially to reproduce the time evolution of the macroscopic physical quantities on the basis of its microscopic simulation data.

Development of advanced electrolytes in Na-ion batteries: application of the Red Moon method for molecular structure design of the SEI layer

“…[59][60][61][62][63][64][65] In addition, the RM method has recently shown a high efficiency to treat the dynamic processes of catalytic polymerization reactions. 66,67 In fact, it can be applicable also to more complicated electrolyte systems such as polymer electrolytes or ionic liquids. On the other hand, it is also important to spell out some modeling limitations for this method, which must be understood carefully to overcome them in the future.…”

Preparation of Pyridylamido Hafnium Complexes for Coordinative Chain Transfer Polymerization

“…In other catalysis [performed with Pd complexes constructed via N-heterocyclic carbene (NHC) ligands], the influence of substituents at the 2,6-position in aryl-N moieties is substantial, and derivatization of the NHC ligand has been carried out by replacing common 2,6-diisopropylphenyl-N parts with 2,6-di(3-pentyl)phenyl-N and 2,6-di(3-heptyl)phenyl-N moieties [30,31]. Much research has also been performed on I [32][33][34][35][36][37][38], and the synthesis of its analogs with the aim to improve the catalytic performance deserves attention [7,29,[39][40][41][42]. Subtle change in the ligand framework sometimes results in dramatic improvement in the polymerization performance and, hence, modification of the substituents has been a main research theme in the development of postmetallocecenes [43][44][45][46][47][48][49].…”

Preparation of Pincer Hafnium Complexes for Olefin Polymerization

“…By performing anionic polymerization of styrene in a one-pot reaction after CCTP with I , it is also possible to synthesize polyolefin-polystyrene block copolymers [23,24,25]. In this context, many studies have been performed to detail I and to improve the catalytic performance by modifying the skeleton of I [26,27,28,29,30,31,32,33,34,35]. With an aim to develop upgraded catalyst for I , we prepared various pincer-type Hf-complexes.…”