Nanosized polymer carriers for metallocene catalysts in heterogeneous olefin polymerization [Elektronische Ressource] / vorgelegt von Yong-Jun Jang

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Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2005
• Nombre de lectures: 24
• Langue: English
• Poids de l'ouvrage: 21 Mo

Extrait

Nanosized Polymer Carriers for Metallocene Catalysts
in Heterogeneous Olefin Polymerization






Dissertation


Zur Erlangung des Grades
„Doktor der Naturwissenschaften“


am Fachbereich Chemie und Pharmazie der
Johannes-Gutenberg-Universität zu Mainz
vorgelegt von






Yong-Jun Jang
geboren in Kwangju, Süd-Korea



Mainz 2005




























Dekan:
1. Berichterstatter:
2. Berichte
Tag der mündlichen Prüfung:

Die vorliegende Arbeit wurde in der Zeit von Juli 2001 bis Juli 2004 im
Max-Planck-Institut für Polymerforschung in Mainz unter Anleitung von
Herrn Prof. Dr. K. Müllen ausgeführt.


























Herrn Professor Dr. K. Müllen danke ich für seine wissenschaftliche und persönliche
Unterstützung sowie für zahlreiche motivierende Diskussionsbereitschaft.









































Dedicated to my wife and family








Table of contents

Table of Contents:

Chapter 1. Introduction…………………….…………………………..…………...……….6
1.1. Polyolefins and olefin polymerization …………………………………….…………..… 6
1.2. Heterogeneous olefin polymerization and supports used for the immobilization of
catalysts……………………………………………………………………………………... 7
1.2.1. Inorganic supports in heterogeneous olefin polymerization ……..……………...……..8
1.2.2. Organic supports in heterogeneous olefin polymerization …………..………………... 9
1.2.3. Fragmentation of the supported catalyst in olefin polymerization …………………... 15
Chapter 2. Motivation and Objectives……..………………..……..……………………... 26
Chapter 3. Nanosized polystyrene (PS) beads as support in heterogeneous ethylene
polymerization …………….…….…………………………….…….………………………31
3.1. Nanosized PS beads functionalized with polyethyleneoxide (PEO) as support in
heterogeneous ethylene polymerization - prepared by PS-PEO block copolymers
……………………………………………………………………………………..………… 31
3.1.1. Preparation of nanosized PS beads functionalized with polyethyleneoxide (PEO) and
the supported catalyst …………………………………………………………………..……31
3.1.2. Ethylene polymerization and characteristics of the PE products…….……………..…35
3.2. Nanosized PS beads functionalized with polyethyleneoxide (PEO) as support in
heterogeneous ethylene polymerization - prepared by PEO functionalized with
styrene………………………………………….…………..…………………………………39
3.2.1. Preparation of nanosized PS beads and the supported catalyst……………….……….39
3.2.2. Ethylene polymerization and characteristics of the PE products…………………...…41
3.2.3. Summary………………………………………….……………………………………44
3.3. Nanosized polystyrene (PS) beads functionalized with polypropyleneoxide (PPO) as
support in olefin polymerization - Ethylene polymerization, propylene polymerization and
copolymerization of ethylene with α-olefin monomers ………………………….………46
3.3.1. Nanosized PS beads functionalized with polypropyleneoxide (PPO) for immobilization
of catalysts in ethylene polymerization…….……………………………………………….46
3.3.1.1. Preparation of nanosized polystyrene (PS) beads functionalized with
polypropyeneoxide (PPO) and the supported catalyst…………………………..……………46
3.3.1.2. Ethylene polymerization……………………………………………………………..49
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3.3.1.3. Characterization of polyethylene products…………………………………..………51
3.3.1.4. Summary……………………………………………………………………………..52
3.3.2. Influence of the concentration of PPO chains on the nanosized particles on the catalyst
activity in ethylene polymerization……………..………………………………………...….54
3.3.2.1. Preparation of nanosized polystyrene (PS) beads functionalized with
polypropyeneoxide (PPO) and the supported catalyst…………………………….……….…54
3.3.2.2. Ethylene polymerization……………………………………………………..………55
3.3.2.3. Characterization of polyethylene products………………………………………......57
3.3.2.4. Kinetic study of ethylene polymerization by the supported catalyst on the different
concentration of PPO functionalized PS beads……………………………………….……...59
3.3.2.5. Summary……………………………………………………………………………..64
3.3.3. Influence of the different preparation method of the supported catalyst on ethylene
polymerization and the product………………..…………………………………………..…65
3.3.3.1. Influence of the ultrasonification method in the supported catalyst system on the
ethylene polymerization and the product…………………………………………………….65
3.3.3.1.1. Preparation of the supported catalyst………………………………..…………….65
3.3.3.1.2. Ethylene polymerization and characteristics of the PE products ....……………... 67
3.3.3.2. Influence of sieving method in the supported catalyst system on the ethylene
polymerization and the product…………………………………………………………...… 70
3.3.3.2.1. Preparation of the supported catalyst………………………………………..…….70
3.3.3.2.2. Ethylene polymerization and characteristics of the PE products ………………....71
3.3.3.3. Summary……………………………………………………………………………..74
3.3.4. Nanosized PS beads functionalized with polypropyleneoxide (PPO) as support in
heterogeneous copolymerization of ethylene with α-olefin monomers………………..…….75
3.3.4.1. Preparation of nanosized polystyrene (PS) beads functionalized with
polypropyeneoxide (PPO) and the supported catalyst………………………………….……75
3.3.4.2. Copolymerization of ethylene with α-olefin monomers…………………...……… 75
3.3.4.3. Characterization of copolymers………………………………………………..…….78
3.3.4.4. Summary……………………………………………………………………………..80
3.3.5. Nanosized PS beads functionalized with polypropyleneoxide (PPO) as support in
heterogeneous propylene polymerization……………………………………………….……82
3.3.5.1. Introduction …………………………………………………………………………82
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3.3.5.2. Preparation support and the supported catalyst……………………………...………83
3.3.5.3 Propylene polymerization………………………………………………………..…..84
3.3.5.3.1. Syndiotactic polypropylene …………………………………………………...…..85
3.3.5.3.2. Elastomeric polypropylene ……………………………………………………….88
3.3.5.4. Summary………………………………………………………………..…………....92
Chapter 4. Influence of the different supports on heterogeneous ethylene
polymerization.......................................................................................................................96
4.1. Introduction……………………………………………….……………………………...96
4.2. Microsized PS beads functionalized with hydroxyl group as a support, the supported
catalyst and ethylene polymerization…………………….………………………………......97
4.2.1. Preparation of the catalyst supported on the microsized PS beads functionalized with
hydroxyl groups ………...…………………………………………………………………98
4.2.2. Preparation of nanosized PS beads functionalized with hydroxy group as support and
the supported catalyst ………………………………………………………………………100
4.2.3. Ethylene polymerization by the catalyst supported on the microsized and nanosized PS
beads and the characterization of PE products ……...…………………………….………..102
4.3. Silica as a support, the supported catalyst and ethylene polymerization……................105
4.3.1 Preparation of silica supported catalyst…………………………………………..…105
4.3.2. Ethylene polymerization by the silica supported catalyst and the characterization of PE
products……………………………………………………………………………….……..107
4.4. A dendritic perylenediimide core functionalized with polyethyleneoxide groups
[PDIG (PEO) ] as support, the supported catalyst and ethylene polymerization ….....…...110 2 16
4.4.1 Preparation of the dendrimer- supported catalyst ………………..…………………...110
4.4.2. Ethylene polymerization by the dendrimer supported catalyst and the characterization
of PE products …………………………………………………………………………….. 112
4.5. Summary………………………………………………….…………………………….115
Chapter 5. Fragmentation of the supported catalyst in ethylene polymerization
………………………………………………………………………………………………117
5.1 Introduction……………………………………………………….……………………..117
5.2. Fragmentation of the catalyst supported on the nanosized PS beads in ethylene
polymerization…………………...………………………………………………….…..… 118
5.2.1. Preparation of supports tagged with dye and functionalized with polyethyleneoxide
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(PEO) and the supported catalyst…………………………………………………………...118
5.2.2. Ethylene polymerization and fragmentation study of the supported catalyst in PE single
particle……………………………………………………………………………………….119
5.2.3. Internal structure and morphology of PE single particle produced by the catalyst
supported on the nanosized PS beads …...……………………………………………….…