Ethylene Polymerization by Thioether Bridged Dinuclear Titanocene Complex

2011 ◽  
Vol 213 ◽  
pp. 354-357 ◽  
Author(s):  
Yu Jing Nie ◽  
Ming Yang

The thioether bridged metallocene complex [(C5H5)Cl2TiC5H4CH2CH2]2S has been synthesized by treating the dilithium salts of the thioether bridged cyclopentadienyl ligand with two equivalents of C5H5TiCl3 and characterized by 1HMNR and elemental analysis. After activation with methylaluminoxane (MAO), the complex was highly active catalysts for homogeneous ethylene polymerization in toluene. The influence of the molar ratio [MAO]/[Cat], the catalyst concentration, time and temperature have been studied systematically. The catalytic activity of 1 is 3.63×105 g PE/mol•Cat•h. Rising the polymerization temperature decreases the catalytic activity for 1. A high concentration of the catalysts drops the catalytic activity as well as the molecular weight of polyethylene for the complex. High temperature gel permeation chromatography (HT-GPC) proves the production of polyethylene with a broad molecular weight distribution (MWD).

2011 ◽  
Vol 213 ◽  
pp. 374-377 ◽  
Author(s):  
Yu Jing Nie ◽  
Ming Yang

The thioether bridged Zirconocene complex [(C5H5)Cl2ZrC5H4CH2CH2]2S has been synthesized by treating the dilithium salts of the thioether bridged cyclopentadienyl ligand with two equivalents of C5H5ZrCl3(DME) and characterized by 1HMNR and elemental analysis. Homogenous ethylene polymerization by this complex has been conducted systematically in the presence of methylaluminoxane (MAO). The influence of the molar ratio [MAO]/[Cat], the catalyst concentration, time and temperature have been studied in detail. The catalytic activity of 1 is 6.46×105 g PE/mol•Cat•h. Higher temperature is favorable for increasing the catalytic activity for 1. A high concentration of the catalysts drops the catalytic activity as well as the molecular weight of polyethylene for the complex. High temperature gel permeation chromatography (HT-GPC) proves the production of polyethylene with a broad molecular weight distribution (MWD).


2011 ◽  
Vol 181-182 ◽  
pp. 804-808
Author(s):  
Yu Jing Nie ◽  
Ming Yang

The phenyl sulfide bridged metallocene complex [(C5H5)Cl2TiC5H4CH2(C6H4-p)]2S has been synthesized by treating the dilithium salts of the phenyl sulfide bridged cyclopentadienyl ligand with two equivalents of C5H5TiCl3 and characterized by 1HMNR and elemental analysis. After activation with methylaluminoxane (MAO), the complex was highly active catalysts for homogeneous ethylene polymerization in toluene. The influence of the molar ratio [MAO]/[Cat], the catalyst concentration, time and temperature have been studied systematically. The highest catalytic activity of 1 is up to 8.30×105 g PE/mol•Cat•h. Rising the polymerization temperature decreases the catalytic activity for 1. High temperature gel permeation chromatography (HT-GPC) proves the production of polyethylene with a broad molecular weight distribution (MWD), which is reached 10.11.


2011 ◽  
Vol 181-182 ◽  
pp. 809-813
Author(s):  
Yu Jing Nie ◽  
Ming Yang

The phenyl sulfide bridged Zirconocene complex [(C5H5)Cl2ZrC5H4CH2(C6H4-p)]2S has been synthesized by treating the dilithium salts of the phenyl sulfide bridged cyclopentadienyl ligand with two equivalents of C5H5ZrCl3(DME) and characterized by 1HMNR and elemental analysis. Homogenous ethylene polymerization by this complex has been conducted systematically in the presence of methylaluminoxane (MAO). The influence of the molar ratio [MAO]/[Cat], the catalyst concentration, time and temperature have been studied in detail. The highest catalytic activity of 1 is up to 13.78×105 g PE/mol•Cat•h. Higher temperature is favorable for increasing the catalytic activity for 1. High temperature gel permeation chromatography (HT-GPC) proves the production of polyethylene with a broad molecular weight distribution (MWD), which is reached 6.02.


1995 ◽  
Vol 60 (3) ◽  
pp. 489-497 ◽  
Author(s):  
Hynek Balcar ◽  
Jan Sedláček ◽  
Marta Pacovská ◽  
Vratislav Blechta

Catalytic activity of the tungsten aryloxo complexes WCl5(OAr) and WOCl3(OAr), where Ar = 4-t-C4H9C6H4, 2,6-(t-C4H9)2C6H3, 2,6-Cl2C6H3, 2,4,6-Cl3C6H2, and 2,4,6-Br3C6H2 in polymerization of phenylacetylene (20 °C, monomer to catalyst molar ratio = 1 000) was studied. The activity of WCl5(OAr) as unicomponent catalysts increases with increasing electron withdrawing character of the -OAr ligand. Addition of two equivalents of organotin cocatalysts (Me4Sn, Bu4Sn, Ph4Sn, Bu3SnH) to WCl5(O-C6H2Cl3-2,4 ,6) has only slight positive effect (slightly higher polymer yield and/or molecular weight of poly(phenylacetylene)s was achieved). However, in the case of WOCl3(O-C6H3Cl2-2, 6) catalyst, it enhances the activity considerably by eliminating the induction period. Poly(phenylacetylene)s prepared with the catalysts studied have weight-average molecular weight ranging from 100 000 to 200 000. They are trans-prevailing and have relatively low molar fraction of monomer units comprised in cyclohexadiene sequences (about 6%).


Catalysts ◽  
2021 ◽  
Vol 11 (7) ◽  
pp. 772
Author(s):  
Yanxiong Liu ◽  
Changhua Hu ◽  
Longchun Bian

The correlation between the occurrence state of surface Pd species of Pd/CeO2 for lean CH4 combustion is investigated. Herein, by using a reduction-deposition method, we have synthesized a highly active 0.5% PdO/CeO2-RE catalyst, in which the Pd nanoparticles are evenly dispersed on the CeO2 nanorods CeO2-R. Based on comprehensive characterization, we have revealed that the uniformly dispersed Pd nanoparticles with a particle size distribution of 2.3 ± 0.6 nm are responsible for the generation of PdO and PdxCe1−xO2−δ phase with –Pd2+–O2−–Ce4+– linkage, which can easily provide oxygen vacancies and facilitate the transfer of reactive oxygen species between the CeO2-R and Pd species. As a consequence, the remarkable catalytic activity of 0.5% Pd/CeO2-RE is related to the high concentration of PdO species on the surface of the catalyst and the synergistic interaction between the Pd species and the CeO2 nanorod.


2018 ◽  
Vol 47 (38) ◽  
pp. 13459-13465 ◽  
Author(s):  
Quande Zheng ◽  
Dejuan Zheng ◽  
Binghao Han ◽  
Shaofeng Liu ◽  
Zhibo Li

Chromium complexes bearing phosphine–imine ligands are highly active for ethylene polymerization and produce HDPE with a high molecular weight.


e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Xiaohui He ◽  
Yiwang Chen ◽  
Yongming Liu ◽  
Muqing Chen ◽  
Shuxian Yu ◽  
...  

AbstractThe polymerizations of n-butyl methylacrylate (nBMA) were carried out using bis(β-ketoamino)nickel(II) complexes (Ni[CH3C(O)CHC(NR)CH3]2: R = phenyl, 1; R = naphthyl, 2) in combination with methylaluminoxane (MAO) in toluene. The effect of parameters such as polymerization temperature, Al/Ni molar ratios, polymerization time, and monomer concentration, on catalytic polymerization activity and polymer molecular weights, were examined in detail. Both of the nickel(II) catalytic systems exhibited moderate activity, and produced P(nBMA) with high molecular weight and relatively broad molecular weight distribution (Mw/Mn=2.0~3.0. The obtained polymer has been characterized by means of FTIR, 1H NMR, 13C NMR, DSC, and WAXD technique and was confirmed to be syndio-rich stereospecific P(nBMA).


Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1114 ◽  
Author(s):  
Yani Luo ◽  
Jian Li ◽  
Derong Luo ◽  
Qingliang You ◽  
Zifeng Yang ◽  
...  

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 106 g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti2L1 with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.


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