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Phillips Cr/Silica Catalyst for Ethylene Polymerization

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Book cover Polyolefins: 50 years after Ziegler and Natta I

Part of the book series: Advances in Polymer Science ((POLYMER,volume 257))

Abstract

The Phillips Cr/silica catalyst, discovered by Hogan and Banks at the Phillips Petroleum Company in the early 1950s, is one of the most important industrial catalysts for polyethylene production. In contrast to its great commercial success during the past half-century, academic progress regarding a basic understanding of the nature of the active sites and polymerization mechanisms is lagging far behind. During the last decade, increasing research efforts have been performed on the Phillips catalyst through various approaches, including spectroscopic methods, polymerization kinetics, heterogeneous model catalysts, homogeneous model catalysts, and molecular modeling. Much deeper mechanistic understanding, together with successive catalyst innovations through modifications of the Phillips catalyst, has been achieved.

An erratum to this chapter can be found at http://dx.doi.org/10.1007/12_2013_259

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Abbreviations

AFM:

Atomic force microscope

BC:

Bis(triphenylsilyl) chromate

BE:

Binding energy

Cp:

Cyclopentadienyl

DCB-d 4 :

1,2-dichlorobenzene-d 4

DEAE:

Diethylaluminum ethoxide

DFT:

Density functional theory

DRIFTS:

Diffuse reflectance infrared Fourier transform spectroscopy

DRS:

Diffuse reflectance spectroscopy

DSC:

Differential scanning calorimetry

EDS:

Energy dispersive spectrometer

EPMA:

Electron probe microanalysis

EPR:

Electron paramagnetic resonance

ESR:

Electron spin resonance

EXAFS:

Extended X-ray absorption fine structure

FTIR:

Fourier transform infrared

FWHM:

Full width at half maximum

GC-MS:

Gas chromatography–mass spectrometry

GPC:

Gel permeation chromatography

HDPE:

High density polyethylene

HMDS:

Hexamethyldisilazane

LA-MS:

Laser ablation–mass spectrometry

LDI-MS:

Laser desorption/ionization–mass spectrometry

m/z :

Mass to charge ratio

MALDI-TOF:

Matrix-assisted laser desorption/ionization time of flight

MAO:

Methylaluminoxane

MAS:

Magic angle spin

MECP:

Minimum energy crossing point

MW:

Molecular weight

M W :

Weight average molecular weight

MWD:

Molecular weight distribution

NMR:

Nuclear magnetic resonance

ONIOM:

Our own n-layered integrated molecular orbital and molecular mechanics

PDI:

Polydispersity index

PE:

Polyethylene

Ph:

Phenyl

PIXE:

Proton induced X-ray emission

POSS:

Polyhedral oligomeric silsesquioxanes

RBS:

Rutherford backscattering spectrometry

RT:

Room temperature

SCB:

Short-chain branch

SEM:

Scanning electron microscopy

SIMS:

Secondary ion mass spectroscopy

SSA:

Successive self-nucleation and annealing

TCB:

1,2,4-Trichlorobenzene

TEA:

Triethylaluminum

TEB:

Triethylborane

TEMPO:

2,2,6,6-Tetramethylpiperidine-N-oxyl

TG-DTA:

Thermogravimetry–differential thermal analysis

THF:

Tetrahydrofuran

TiBA:

Triisobutylaluminum

T m :

Melting temperature

TPD-MS:

Temperature-programmed desorption–mass spectrometry

TPR:

Temperature-programmed reduction

TPS:

Triphenylsilanol

TREF:

Temperature rising elution fractionation

UV-vis:

Ultraviolet–visible

XANES:

X-ray absorption near edge structure

XAS:

X-ray absorption spectroscopy

XPS:

X-ray photoelectron spectroscopy

XRD:

X-ray diffraction

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Acknowledgements

We are gratefully thankful for the financial support by the National Natural Science Foundation of China (No. 21104019 and 21274040), the National High Technology Research and Development Program 863 (2012AA040306), and the Shanghai Science and Technology Commission (Key Project for Basic Research 10JC1403700). This work is also financially supported by the Fundamental Research Funds for the Central Universities, Research Program of Introducing Talents of Discipline of University (B08021).

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Authors and Affiliations

  1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai, 200237, PR China

    Ruihua Cheng, Zhen Liu, Lei Zhong, Xuelian He, Pengyuan Qiu & Boping Liu

  2. School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japan

    Minoru Terano

  3. Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa, 32000, Israel

    Moris S. Eisen

  4. Department of Chemical Engineering, University of California, Santa Barbara, CA, 93106-5080, USA

    Susannah L. Scott

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  1. Ruihua Cheng
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  2. Zhen Liu
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  3. Lei Zhong
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  4. Xuelian He
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  5. Pengyuan Qiu
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  9. Boping Liu
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Correspondence to Boping Liu .

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  1. Dept. of Chemistry Inst. for Techn. and Macromol. Chemistry, University of Hamburg, Hamburg, Germany

    Walter Kaminsky

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Cheng, R. et al. (2013). Phillips Cr/Silica Catalyst for Ethylene Polymerization. In: Kaminsky, W. (eds) Polyolefins: 50 years after Ziegler and Natta I. Advances in Polymer Science, vol 257. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2013_222

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