Fundamentals of controlled/living radical polymerization. Tsarevsky and Brent S. Sumerlin, Nicolay V. Tsarevsky and Brent S. Sumerlin

378 Pages·2013·8.139 MB·English

Fundamentals of Controlled/Living Radical Polymerization
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RSC Polymer Chemistry Series
Series Editors:
Professor Ben Zhong Tang (Editor-in-Chief), The Hong Kong University of
Science and Technology, Hong Kong, China
1 Professor Alaa S. Abd-El-Aziz, University of Prince Edward Island, Canada
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5- ProfessorJianhua Dong,NationalNaturalScience FoundationofChina,China
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39/ 1: Renewable Resources for Functional Polymers and Biomaterials
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org | 4: Fundamentals of Controlled/Living Radical Polymerization
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Fundamentals of Controlled/
Living Radical Polymerization
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81 Nicolay V Tsarevsky
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9/ Department of Chemistry, Southern Methodist University, Dallas, TX, USA
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c.or Department of Chemistry, University of Florida, Gainesville, FL, USA
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F Preface
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0.1 There is little doubt the advent of controlled/living radical polymerization
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oi: (CRP) has revolutionized modern polymer science. Perhaps more than any
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g | syntheticdevelopmentofthelastseveraldecades,CRPhasunlockedaccesstoa
or plethora of new functional and well-defined polymers to address a variety of
c.
s.rs complexapplications.Previouslyconsideredusefulforprimarilythefacileand
ub rapid preparation of high molecular weight polymers for mostly commodity
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htt specialtymaterialsbasedon(co)polymersthatarewell-defined,havecontrolled
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3 o molecular weights and end group functionality, complex topologies, and
d 01 predefined segment sequences (e.g., block copolymers).
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d weight polymers, precise control of chain length remained difficult. External
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diverse family of CRP techniques developed over the last 2–3 decades now
allows access to polymers of a specific chain length that can be derived from
virtually any vinyl monomer polymerizable by a radical method.
Conventional radical polymerization had limited success in the preparation
of polymers with specific chain-end functional and/or reactive groups.
Although certain functionalized radical initiators showed some potential, the
rangeoffunctionalgroupsthatcouldbeattachedefficientlytoeitherendofthe
macromolecules was relatively narrow. Further, due to the ever-present
terminationandtransferreactions,whichrapidly‘‘kill’’thepropagatingchains,
itisvirtuallyimpossibletopreparesamplesinwhichnearlyallmacromolecules
arechain-end-labeled.Incontrast,CRPmethodshaveprovedverypowerfulin
the synthesis of polymers containing either identical or different a- and
RSCPolymerChemistrySeriesNo.4
FundamentalsofControlled/LivingRadicalPolymerization
EditedbyNicolayVTsarevskyandBrentSSumerlin
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
v
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vi Preface
o-chain-endfunctionalgroups.ThesynthesisofcompositematerialsbyCRPis
also straightforward.
Oneofthekeybenefitsofclassicalradicalpolymerizationisthefacilitywith
which many monomers can be incorporated into a single chain by copoly-
merization. Depending on the relative reactivity of the comonomers, random,
05 alternatingandblockysequencescanbeachieved.However,blockcopolymers
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FP with well-defined junction points linking segments of differing repeat units are
5-
2 nearly impossible to prepare directly by conventional radical polymerization.
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3 While it was possible to prepare block copolymers by coupling two end-
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4 functional homopolymers or by polymerization from homopolymers
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81 terminatedwithamoietythatallowedasubsequentpolymerizationstep,facile
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9/9 access to block copolymers was not achieved by a radical mechanism prior to
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0 the development of controlled radical methods. Since then, an enormous
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10. number of new block copolymers have been prepared by CRP, and this has
doi: provided access to a variety of new materials with potential applications as
g | drug delivery agents, cosmetics, coatings, adhesives, thermoplastic elastomers,
or
c. etc.Additionally,thecopolymerizationofmonomerswithdifferentreactivities
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bs.r under CRP conditions yields gradient copolymers, in which the composition
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d 013 materials in various fields, such as surfactants, degradable polymers, etc.
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he prepared by CRP. Stars, combs, and brushes represent only a fraction of
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property relationships.
Many of the aforementioned characteristics of CRP are in common with
those of previously developed (pseudo)living ionic polymerization techniques.
However, it is the relative ease with which CRP can be employed to achieve
these characteristics that has led to the continued success and growth of the
field.Indeed,becausemostofthemethodsdescribedinthechaptersthatfollow
can be conducted under relatively non-stringent conditions in a variety of
solventsandatawiderangeoftemperatures,thebarriertoentrytothefieldis
minimal. Precision polymer synthesis is now possible in laboratories without
access to expensive experimental equipment or extensive expertise.
It is important to remember that the CRP techniques are based on the
success achieved over many years in the areas of living ionic polymerizations.
ThesuccessofSzwarcandothersinrecognizingthefar-reachingutilityofliving
anionic polymerization led many to pursue the goal of polymerization control
during other chain growth methods. Molecular weight and end group control
in cationic polymerization was subsequently achieved by introduction of the
concept of dormant-active equilibration (i.e., ‘‘reversible deactivation’’) that
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Preface vii
kinetically limited the extent of chain breaking reactions by rendering a
significant fraction of chains dormant at any given time. Unfortunately, ionic
polymerizations are applicable only to a relatively narrow range of monomers
and required stringent reaction conditions (e.g., absence of moisture, carbon
dioxide, and many other impurities often encountered in commercially
05 available monomers and solvents). Owing to significant differences in the
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FP reactivity ratios of the ionically polymerizable monomers, copolymerization
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2 reactionsareoftenchallenging,whichlimitsthenumberofaccessiblematerials.
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3 For a relatively long time, it was considered that radical polymerizations that
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4 were living or atleastresembledlivingionic processwereimpossibletodesign
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81 due to fast termination reactions between the propagating radicals. It was
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9/9 thought that living radical polymerization could only be achieved in system
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0 where the mobility of the growing radicals was drastically diminished by, for
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10. instance,carryingoutthepolymerizationsinveryviscousmediaandpreferably
doi: atlowtemperatures(which notonlyincreasestheviscositybutalso minimizes
g | transfer). Of course, such approaches were not particularly practical. The
or
c. principle of reversible deactivation of propagating radicals was extended to
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bs.r radical polymerization in the 1980s and proved to be of tremendous utility in
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n various CRP processes. The fundamental aspects such as kinetics, thermo-
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he molecular weight (determined by the ratio of monomer to initiator), narrow
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copolymers, etc. Owing to the ability to control numerous molecular
parameters and due to the fact that radical polymerizations with reversible
deactivationresemblecloselytheclassicallivingionicpolymerizations,wehave
adopted the term controlled/living radical polymerization in this book.
WehopethisbookprovidesinsightintothecurrentstateoftheartinCRPwhile
also giving historical perspective to the field. While many other books have
focusedoncontrolled/livingpolymerizations,includingCRP,andhaveprovided
extensiveinsightintothematerialsthatcanbepreparedtherefrom,ourintenthere
is to elucidate the fundamentals governing the most common types of CRP. In
many cases, particular attention is dedicated to the kinetic and thermodynamic
factorsthateffectpolymerizationcontrol.Wehopethiscollectionwillbeusefulto
bothexpertsandnewcomerstothisrapidlyexpandingfield.
Nicolay V. Tsarevsky
Southern Methodist University, Dallas
Brent S. Sumerlin
University of Florida
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9/ Chapter 1 Kinetics and Thermodynamics of Radical Polymerization 1
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org | 1.2 Initiation 2
sc. 1.2.1 Thermal Initiation 4
bs.r 1.2.2 Photoinitiation 4
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on 1.3 Propagation 8
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1.4.4 Transfer to Polymer 22
1.5 Termination 25
1.5.1 Combination versus Disproportionation 25
1.5.2 Termination Rate 28
1.5.3 Monomer Conversion Dependence 29
1.5.4 Chain-lengthDependentTermination(CLD-T) 31
1.5.5 Combined Chain-Length and Monomer
Conversion Dependence 35
1.5.6 Temperature and Pressure Dependence 36
1.5.7 Solvent Effects 37
RSCPolymerChemistrySeriesNo.4
FundamentalsofControlled/LivingRadicalPolymerization
EditedbyNicolayVTsarevskyandBrentSSumerlin
rTheRoyalSocietyofChemistry2013
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
ix
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x Contents
1.6 Rate of Polymerization 38
1.7 The Chain Length Distribution 42
1.8 Thermodynamics 48
References 51
09 Chapter 2 Fundamental Aspects of Living Polymerization 60
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0 2.5 Propagation Kinetics of Reversible-Deactivation
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1 Polymerizations 65
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org | Polymerizations 67
sc. 2.7 Rate of Initiation 70
bs.r 2.8 Polydispersity of Living Polymers 71
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on References 75
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Down 25 Mehmet Atilla Tasdelen and Yusuf Yagci
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3.3 Iniferters 84
3.3.1 Thermal Iniferters 84
3.3.2 Photoiniferters 87
3.3.3 Redox Iniferters 88
3.4 Applications 92
3.4.1 Telechelic Polymers by Iniferters 92
3.4.2 Complex Macromolecular Architectures by
Iniferters 92
3.4.4 Surface Modification by Iniferters 98
3.5 Conclusions 101
Abbreviations 102
References 103
Chapter 4 Controlled/Living Radical Polymerization Mediated by
Stable Organic Radicals 112
Peter Nesvadba
4.1 Introduction 112