Hyperverzweigte Lacton-Copolymere [Elektronische Ressource] : enzymatische Synthese, Charakterisierung und Darstellung strukturierter Polymernetzwerke = (Hyperbranched lactone copolymers by enzyme catalysis) / Ingo Th. Neuner

Ingo Th. Neuner

Informations

• Publié par: johannes_gutenberg-universitat_mainz
• Publié le: 01 janvier 2005
• Nombre de lectures: 27
• Poids de l'ouvrage: 2 Mo

Extrait

HYPERVERZWEIGTE LACTON-COPOLYMERE:
ENZYMATISCHE SYNTHESE, CHARAKTERISIERUNG UND DARSTELLUNG
STRUKTURIERTER POLYMERNETZWERKE


(HYPERBRANCHED LACTONE COPOLYMERS BY ENZYME CATALYSIS:
SYNTHESIS, CHARACTERIZATION AND PREPARATION OF STRUCTURED
POLYMER NETWORKS)






Dissertation
zur Erlangung des Grades
“Doktor der Naturwissenschaften“


am Fachbereich 09
Chemie, Pharmazie und Geowissenschaften
der Johannes Gutenberg-Universität
in Mainz


Ingo Th. Neuner
geboren in
Heidenheim an der Brenz

Mainz, 2005

Dekan: N.N.
1. Berichterstatter: N.N.
2. Berichters
Tag der mündlichen Prüfung: 21. November 2005
















meinen Eltern












Die experimentellen Untersuchungen zu dieser Arbeit wurden im Januar 2002 am Institut
für Makromolekulare Chemie der Albert-Ludwigs-Universität zu Freiburg, begonnen, ab
September 2002 am Institut für Organische Chemie der Johannes Gutenberg-Universität
zu Mainz fortgeführt und im Juni 2005 vollendet.
1.1 Branched Polymers

TABLE OF CONTENTS
1 GENERAL INTRODUCTION 1
1.1 Branched Polymers 1
1.2 Characteristic Properties of Hyperbranched Polymers 4
1.3 Applications of Hyperbranched Polymers 5
1.4 Degree of Branching 7
1.5 Concurrent AB/AB Polymerization 8 2
1.6 Hyperbranched Poly(ε-caprolactone) 9
2 OBJECTIVE 13
2.1 Introduction 13
2.2 Hyperbranched Poly(ε-caprolactone)s 14
2.3 Reknitting as a New Method of Synthesizing Hyperbranched Poly(ε-caprolactone)s 15
2.4 Methacrylated Hyperbranched Poly(ε-caprolactone)s as Multi-functional Crosslinkers 16
2.5 Hyperbranching Polymerization of Other Lactones or Carbonates 16
3 HYPERBRANCHED POLY(ε-CAPROLACTONE)S 19
3.1 Synthesis 19
3.2 Characterization 21
3.2.1 NMR Experiments 21
3.2.2 VPO, GPC, GPC-Online Viscometry and Solution Viscometry 23
3.2.3 MALDI-TOF Mass Spectroscopy 28
3.2.4 Physical Properties 29
3.3 Hyperbranched Poly(ε-caprolactone) by Polymerization in Solution 30
3.4 Hyperbranched Poly(ε-caprolactone) by Bulk Polymerization 31
3.4.1 Reaction Kinetics 31
3.4.2 Degree of Branching 32
3.4.3 Increasing Molecular Weights by Advanced Water Removal 41
3.5 Parameter Optimization for Synthesis on the kg-scale 42
3.5.1 Influence of the Concentration of Novozyme 435 on the Product 42
3.5.2 Enzyme Regeneration and Enzyme Leaching 43
3.6 Preparation of hb-Poly(ε-caprolactone)s on the kg-scale 45
3.7 Conclusions 47

I1 General Introduction

4 REKNITTING AS NOVEL ROUTE TO HYPERBRANCHED
POLY(ε-CAPROLACTONE) 49
4.1 Preparation of hb-Poly(ε-caprolactone) from the Linear Analogue 49
4.2 Characterization 49
4.3 Results and Discussion 50
4.4 Conclusions 58
5 STRUCTURED POLYMER NETWORKS 61
5.1 Introduction 61
5.2 Methacrylation of hb-PCL 62
5.3 UV-Curing / Networks 66
5.4 Dynamic Mechanical Testing and Tensile Tests 67
5.5 Swelling Experiments 74
5.6 Conclusions 76
6 HYPERBRANCHING POLYMERIZATION OF ANALOGOUS LACTONES
AND CARBONATES 79
6.1 Introduction 79
6.2 Screening of Cyclic Esters for Hyperbranching Polymerization 80
6.3 Hyperbranched Poly(δ-Valerolactone)s 81
6.4 Hyperbranched Poly(trimethylene carbonate)s 86
7 SUMMARY & PERSPECTIVES 91
7.1 Hyperbranched Poly(ε-caprolactone)s 91
7.2 Hyperbranched Poly(ε-caprolactone)s on the kg-scale 93
7.3 “Reknitting” of Linear into Hyperbranched Poly(ε-caprolactone) 94
7.4 Structured Polymer Networks 96
7.5 Hyperbranching Copolymerization of Analogous Lactones and Carbonates 98
7.6 Perspectives 99
8 EXPERIMENTAL 101
8.1 Materials 101
8.2 Monomer Synthesis: Trimethylene carbonate (TMC) 101
8.3 Polymerization Apparatus 102
8.3.1 Carrousel Reactor for Parallel Synthesis 102
8.3.2 Scale-Up Reactor for Batch Synthesis 102
8.4 Linear Poly(ε-caprolactone) 103

II 1.1 Branched Polymers

8.5 Hyperbranched Poly(ε-caprolactone)s 104
8.5.1 Polymerization in Solution 104
8.5.2 Polymerization in Bulk 104
8.6 Reknitting of Commercial Linear Poly(ε-caprolactone) 105
8.7 Optimization of Bulk hb-PCL Synthesis 105
8.8 Methacrylation of Hyperbranched Poly(ε-caprolactone)s 106
8.9 UV-Cross-linking of methacrylated hb Poly(ε-caprolactone)s
8.10 Screening Experiments 107
8.11 Hyperbranched Poly(δ-valerolactone)s 107
8.12 Hyperbranched Poly(trimethylene carbonate)s 108
8.13 General Characterization 108
8.13.1 DSC 108
8.13.2 MALDI-TOF Mass Spectrometry 108
8.13.3 NMR 109
8.13.4 VPO 109
8.13.5 GPC 109
8.13.6 Viscosity in Solution 110
8.13.7 SDS-Page Electrophoresis 110
8.13.8 Dynamic Mechanical Analysis (DMA) 110
8.13.9 Tensile Tests 110
9 BIBLIOGRAPHY 111
10 APPENDIX – SUPPORTING INFORMATION 117
10.1 Chapter 4: Fractionation of hb-PCL Prepared by Rekniting 117
10.2 Chapter 5: Polymer Networks – Dynamic Mechanical Analysis 120
10.3 Chapter 5: Polymer Networks – Tensile Tests 122



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