Hyperbranched Polymers: Macromolecules in between Deterministic Linear Chains and Dendrimer Structures

304 Pages·2015·10.603 MB·English

by  Albena Lederer, Walther Burchard, Ben-Zhong Tang

Hyperbranched Polymers
Macromolecules in between Deterministic Linear Chains and
Dendrimer Structures
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RSC Polymer Chemistry Series
Editor-in-Chief:
Professor Ben Zhong Tang, The Hong Kong University of Science and
Technology, Hong Kong, China
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FP Series Editors:
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6 Professor Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
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2 Professor Stephen Craig, Duke University, USA
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8 ProfessorJianhuaDong,NationalNaturalScienceFoundationofChina,China
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8 Professor Toshio Masuda, Shanghai University, China
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9/ Professor Christoph Weder, University of Fribourg, Switzerland
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1 Titles in the Series:
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d 1: Renewable Resources for Functional Polymers and Biomaterials
org | 2: Molecular Design and Applications of Photofunctional Polymers and
sc. Materials
bs.r 3: Functional Polymers for Nanomedicine
u
p://p 4: Fundamentals of Controlled/Living Radical Polymerization
htt 5: Healable Polymer Systems
on 6: Thiol-X Chemistries in Polymer and Materials Science
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1 7: Natural Rubber Materials: Volume 1: Blends and IPNs
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12:15:34. on 01 July 2 1890:::NCPooalntyujmuragelariRtceudMbPbaoeterlyrMmiaalestreswr:iiAathlsP:ArVancottilimucmaiclerGo2ub:iidaCleoAmtocptiSovysintiytte:hsFersaoinsmd NSyanntohceosmisptoosites
d Applications
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sh 11: Phosphorus-Based Polymers: From Synthesis to Applications
ubli 12: Poly(lactic acid) Science and Technology: Processing, Properties,
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Additives and Applications
13: Cationic Polymers in Regenerative Medicine
14: Electrospinning: Principles, Practice and Possibilities
15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications
16: Hyperbranched Polymers: Macromolecules in between Deterministic
Linear Chains and Dendrimer Structures
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Hyperbranched Polymers
Macromolecules in between Deterministic
Linear Chains and Dendrimer Structures
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26 Albena Lederer
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1 Leibniz Institute of Polymer Research, Dresden, Germany
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10. Walther Burchard
doi: Albert-Ludwigs-University Freiburg, Freiburg, Germany
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he Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor
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F Preface
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1 Hyperbranchedmacromoleculesareanintegralpartofnature.SinceFlory’s
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oi:1 first successful effort to calculate such structures it took several decades
g | d beforetheycouldbesynthesized.Inthe1980sthefirstsuccessinpreparing
c.or polymers with AB2 monomers was reported.
s Some40yearsagouncontrolledbranchingwasclassifiedasanundesired
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b side-effect of polymerization, causing a delay in network formation. At pre-
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htt potentials seem to be endless. Countless numbers of functional groups
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o fascinated chemists, permitting modifications which are used for different
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01 applications, such as processing or coatings. They also possess significant
2:15:35. 01 July 2 pthoetecnotmialpainctssetnrsuocrtiucrse, dcaiaugsneossaticdse,ccraetaasleysoisf athnedvtihsecroaspiteyutwichse.nInapapdldieitdioans,
1on additives to melts.
d Challenging requirements for suitable tailoring of material properties
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blis generates the need to understand the molecular characteristics of hyper-
u branched macromolecules. The discovery potential in this area is huge,
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taking into account the statistical character and manifold modification
possibilities. Academic interest in hyperbranched molecules has continu-
ously increased during the past 20 years since the discovery by Kim and
Webster. Morethan700researcharticlesperyearregardinghyperbranched
polymers are reported, with a continuously growing tendency.
Since Flory’s fundamental work major efforts have been undertaken to
synthesize dendritic structures. With the appearance of hyperbranched
molecules many new routes for applications have opened. Yet, only a few
researchgroupsattempttounderstandtheirpropertiesbysuitabletheories.
Preparative physical chemists commonly possess a widespread experi-
mental experience but lack knowledge in modern theory. Vice versa,
RSCPolymerChemistrySeriesNo.16
HyperbranchedPolymers:MacromoleculesinbetweenDeterministicLinearChainsand
DendrimerStructures
ByAlbenaLedererandWaltherBurchard
rAlbenaLedererandWaltherBurchard2015
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
View Online
vi Preface
theoreticianstendtohaveinsufficientinsightintothefeasibilityofpolymer
sythesisforspecialstructures.Whenthepresenttwoauthorscametogether
theyrecognizedthattheirexperienceoverlapped.Collaborationoverseveral
years led to the idea to assemble this knowledge in a book.
In this book we are attempt to present the knowledge of physical chem-
5 istrycharacterizationinasuitablemathematicalscheme.Themainproblem
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8- the formation of large structures. As far as we know, this book is the first
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2 We hope that our book will support a new trend in future studies of
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1 hyperbranched polymers.
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c. Chapter 1 Introduction 1
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2.1.1 Contraction Factors 22
2.1.2 Degree of Branching 24
2.1.3 CorrelationBetweentheDegreeofBranching
and Contraction 27
2.2 Determination of the Degree of Branching 28
2.2.1 Analysis by Spectroscopic Approaches 28
2.2.2 Influence of the Synthetic Approach on the
Degree of Branching 30
2.2.3 Side Reactions and the Degree of Branching 33
References 35
RSCPolymerChemistrySeriesNo.16
HyperbranchedPolymers:MacromoleculesinbetweenDeterministicLinearChainsand
DendrimerStructures
ByAlbenaLedererandWaltherBurchard
rAlbenaLedererandWaltherBurchard2015
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
vii
View Online
viii Contents
Chapter 3 Control over the Conformation of Dendritic Polymers 39
3.1 Introduction 39
3.2 Tuning the Degree of Branching 42
3.2.1 The AB þAB Approach 42
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d 5.3 The Viscosity Behaviour of Dendritic Polymers 97
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Pu 5.3.2 Hyperbranched Polymers 99
5.3.3 Pseudo-dendrimers 102
5.3.4 Dendronized Polymers 105
5.4 Influence of Chemical Structure on Viscosity
Behaviour 107
5.4.1 Influence of the Backbone Character 107
5.4.2 Influence of Functionality 110
5.5 Influence of Segmental Density on Viscosity and
Scaling Characteristics 115
5.5.1 Gradually Increasing Statistical Branching 115
5.5.2 Pseudo-dendrimers with Increasing
Generation 124
References 132
Chapter 6 Size Determination by Scattering Techniques 136
6.1 Introduction 136
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Contents ix
6.2 The Search for Non-invasive Structure
Characterization 137
6.2.1 Microscopy 138
6.2.2 Rheology 139
6.2.3 Sedimentation by Ultracentrifugation 140
07 6.2.4 Application of Light 140
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d 6.3.5 Summary: Static Light Scattering 154
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Stochastic Processes 167
6.5.4 Time Correlation Functions 168
6.5.5 Comment on Averages and the Effect of
External Forces 169
6.5.6 The Time Correlation Function in Dynamic
Light Scattering 171
6.5.7 Flexible Particles: Linear and Branched
Macromolecules in Solution 176
6.5.8 Small Particles: Proteins 177
6.5.9 Polydispersity and the Effects of Cluster
Formation 179
6.5.10 Electrophoretic/Dynamic Light
Scattering 180
6.5.11 Concentration Dependence 183
6.5.12 Summary: Dynamic Light Scattering 185
6.6 Effects of Heterodyne Light Scattering 185
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x Contents
6.7 Appendix: Aspects of Modern Theory of Segmental
Dynamics 186
6.8 Recommended Literature 189
References 189
07 Chapter7 ModelCalculationofDifferentHyperbranchedStructures 193
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7.4.2 The Flory Expansion Factor 211
7.4.3 Size Distribution of Real Chains 212
7.4.4 The Particle Scattering Factor, P(q) 213
7.4.5 FractalApproachtoFitsofMeasuredParticle
Scattering Factors 215
7.4.6 The Radius of Gyration and Hydrodynamic
Radius of Branched Macromolecules in
Good Solvents 220
7.5 Summary 224
References 225
Chapter 8 Scaling Conception and Interpretation of Structural
Parameters and Scattering Experiments 227
8.1 Molecular Properties in a Global Scale 227
8.1.1 General Comments 227
8.1.2 Molecular Parameters 228