Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene
© 2017 Density functional theory (DFT) calculations have been carried out to investigate the ethylene insertion pathway using a Ziegler-Natta catalyst in the absence and presence of electron donor (ED) systems on the (1 1 0) MgCl2surface. The coadsorptions of four different EDs i.e. Si(OEt)mCln(m + ...
Saved in:
Main Authors: | , , , , , , , |
---|---|
Format: | Journal |
Published: |
2018
|
Subjects: | |
Online Access: | https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85018624812&origin=inward http://cmuir.cmu.ac.th/jspui/handle/6653943832/56731 |
Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
Institution: | Chiang Mai University |
id |
th-cmuir.6653943832-56731 |
---|---|
record_format |
dspace |
spelling |
th-cmuir.6653943832-567312018-09-05T03:53:07Z Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene Sutiam Kruawan Manussada Ratanasak Rungroj Chanajaree Thanyada Rungrotmongkol Oraphan Saengsawang Vudhichai Parasuk Nawee Kungwan Supot Hannongbua Biochemistry, Genetics and Molecular Biology Chemistry Physics and Astronomy © 2017 Density functional theory (DFT) calculations have been carried out to investigate the ethylene insertion pathway using a Ziegler-Natta catalyst in the absence and presence of electron donor (ED) systems on the (1 1 0) MgCl2surface. The coadsorptions of four different EDs i.e. Si(OEt)mCln(m + n = 4) were investigated. The presence of Si(OEt)4on the (1 1 0) MgCl2surface with the preferential bidentate mode was found to have the strongest adsorption energy (ΔEads). The potential energy surface (PES) map indicated that the reaction mechanism of the ethylene insertion into the Ti[sbnd]C bond on the (1 1 0) Mg13Cl26.TiCl3-CH2CH3surface is pseudo-concerted. As the differences in the intrinsic activation energies (ΔEa) obtained from all systems are so small, this energy cannot be used to fully explain the significant changes in the rates of the ethylene insertion reaction observed when an ED is employed. Here, the apparent activation energy (ΔΔEaa) was calculated using the PBE functional and the 6-31G(d, p) basis set for C, H, O, Mg and Cl, and the LANL2DZ basis set with an ECP function for the Ti atom. All EDs presented in this work in the ethylene insertion reaction can significantly reduce the apparent energy barrier when compared to an absence of any ED system. The obtained ΔΔEaafor the four ED complexes were found to decrease in the following order: SiOEtCl3 > Si(OEt)2Cl2 > Si(OEt)3Cl > Si(OEt)4. The obtained data lead to the conclusion that Si(OEt)4is the most suitable ED to increase the productivity of PE in the presence of alkoxysilane. 2018-09-05T03:29:31Z 2018-09-05T03:29:31Z 2017-07-15 Journal 2210271X 2-s2.0-85018624812 10.1016/j.comptc.2017.04.002 https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85018624812&origin=inward http://cmuir.cmu.ac.th/jspui/handle/6653943832/56731 |
institution |
Chiang Mai University |
building |
Chiang Mai University Library |
country |
Thailand |
collection |
CMU Intellectual Repository |
topic |
Biochemistry, Genetics and Molecular Biology Chemistry Physics and Astronomy |
spellingShingle |
Biochemistry, Genetics and Molecular Biology Chemistry Physics and Astronomy Sutiam Kruawan Manussada Ratanasak Rungroj Chanajaree Thanyada Rungrotmongkol Oraphan Saengsawang Vudhichai Parasuk Nawee Kungwan Supot Hannongbua Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
description |
© 2017 Density functional theory (DFT) calculations have been carried out to investigate the ethylene insertion pathway using a Ziegler-Natta catalyst in the absence and presence of electron donor (ED) systems on the (1 1 0) MgCl2surface. The coadsorptions of four different EDs i.e. Si(OEt)mCln(m + n = 4) were investigated. The presence of Si(OEt)4on the (1 1 0) MgCl2surface with the preferential bidentate mode was found to have the strongest adsorption energy (ΔEads). The potential energy surface (PES) map indicated that the reaction mechanism of the ethylene insertion into the Ti[sbnd]C bond on the (1 1 0) Mg13Cl26.TiCl3-CH2CH3surface is pseudo-concerted. As the differences in the intrinsic activation energies (ΔEa) obtained from all systems are so small, this energy cannot be used to fully explain the significant changes in the rates of the ethylene insertion reaction observed when an ED is employed. Here, the apparent activation energy (ΔΔEaa) was calculated using the PBE functional and the 6-31G(d, p) basis set for C, H, O, Mg and Cl, and the LANL2DZ basis set with an ECP function for the Ti atom. All EDs presented in this work in the ethylene insertion reaction can significantly reduce the apparent energy barrier when compared to an absence of any ED system. The obtained ΔΔEaafor the four ED complexes were found to decrease in the following order: SiOEtCl3 > Si(OEt)2Cl2 > Si(OEt)3Cl > Si(OEt)4. The obtained data lead to the conclusion that Si(OEt)4is the most suitable ED to increase the productivity of PE in the presence of alkoxysilane. |
format |
Journal |
author |
Sutiam Kruawan Manussada Ratanasak Rungroj Chanajaree Thanyada Rungrotmongkol Oraphan Saengsawang Vudhichai Parasuk Nawee Kungwan Supot Hannongbua |
author_facet |
Sutiam Kruawan Manussada Ratanasak Rungroj Chanajaree Thanyada Rungrotmongkol Oraphan Saengsawang Vudhichai Parasuk Nawee Kungwan Supot Hannongbua |
author_sort |
Sutiam Kruawan |
title |
Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
title_short |
Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
title_full |
Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
title_fullStr |
Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
title_full_unstemmed |
Ethylene insertion in the presence of new alkoxysilane electron donors for Ziegler-Natta catalyzed polyethylene |
title_sort |
ethylene insertion in the presence of new alkoxysilane electron donors for ziegler-natta catalyzed polyethylene |
publishDate |
2018 |
url |
https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=85018624812&origin=inward http://cmuir.cmu.ac.th/jspui/handle/6653943832/56731 |
_version_ |
1681424746916347904 |