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Polymers with Complex Architecture by Living Anionic Polymerization

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Polymers with Complex Architecture by Living Anionic Polymerization Chem. Rev. 2001, 101, 3747−3792 3747 Polymers with Complex Architecture by Living Anionic Polymerization Nikos Hadjichristidis,* Marinos Pitsikalis, Stergios Pispas, and Hermis Iatrou Department of Chemistry, University of Athens, Panepistimiopolis Zografou, 15771 Athens, Greece Received January 31, 2001 Contents weight and compositional polydispersity. Later star homopolymers and block copolymers, the simplest I. Introduction 3747 complex architectures, were prepared. Polymer physi- II. Star Polymers 3747 cal chemists and physicists started studying the A. General Methods for the Synthesis of Star 3747 solution3 and the bulk properties of these materials.4 Polymers The results obtained forced the polymer theoreticians 1. Multifunctional Initiators. 3749 either to refine existing theories5 or to create new 2. Multifunctional Linking Agents 3751 ones.6 Over the past few years, polymeric materials 3. Use of Difunctional Monomers 3754 having more complex architectures have been syn- B. Star−Block Copolymers 3754 thesized. The methods leading to the following com- C. Functionalized Stars 3755 plex architectures will be presented in this review: 1. Functionalized Initiators 3755 (1) star polymers and mainly asymmetric and mik- R 2. Functionalized Terminating Agents 3756 toarm stars; (2) comb and ,ω-branched polymers; (3) D. Asymmetric Stars 3757 cyclic polymers and combinations of cyclic polymers with linear chains; and (4) hyperbranched polymers. 1. Molecular Weight Asymmetry 3757 Emphasis has been placed on chemistry leading to 2. Functional Group Asymmetry 3760 well-defined and well-characterized polymeric mate- 3. Topological Asymmetry 3761 rials. Complex architectures obtained by combination E. Miktoarm Star Polymers 3761 of anionic polymerization with other polymerization 1. Chlorosilane Method 3761 methods are not the subject of this review. 2. Divinylbenzene Method 3766 3. Diphenylethylene Derivative Method 3766 II. Star Polymers 4. Synthesis of Miktoarm Stars by Other 3770 Methods Star polymers are branched polymers consisting of III. Comb-Shaped Polymers 3771 several linear chains linked to a central core. The synthesis of star polymers has been the subject of A. “Grafting Onto” 3771 numerous studies since the discovery of living anionic B. “Grafting From” 3773 polymerization.7-10 C. “Grafting Through” 3774 IV. Block−Graft Copolymers 3775 A. General Methods for the Synthesis of Star V. R,ω-Branched Architectures 3776 Polymers VI. Cyclic Polymers 3778 A. Cyclic Homopolymers from Precursors with 3780 Three general synthetic methods have been devel- Homodifunctional Groups oped, as outlined in Scheme 1: 1. Cyclic Homopolymers 3780 Scheme 1 2. Cyclic Block Copolymers 3782 3. Tadpole and Bicyclic Polymers 3784 B. Cyclic Homopolymers from Precursors with 3786 Heterodifunctional Groups C. Catenanes 3786 VII. Hyperbranched Architectures 3787 VIII. Concluding Remarks 3790 IX. List of Symbols and Abbreviations 3790 X. References 3790 I. Introduction Immediately after the discovery of the living char- acter1 of anionic polymerization,2 polymer chemists started synthesizing well-defined linear homopoly- mers and diblock copolymers with low molecular 10.1021/cr9901337 CCC: $36.00 © 2001 American Chemical Society Published on Web 11/21/2001 3748 Chemical Reviews, 2001, Vol. 101, No. 12 Hadjichristidis et al. Marinos Pitsikalis received his B.Sc. and Ph.D. from the University of Hermis Iatrou received his B.Sc. and Ph.D. from the University of Athens, Athens, Greece in 1989 and 1994, respectively. His postdoctoral research Greece, in 1989 and 1993, respectively. He did postdoctoral research at was done at the University of Alabama at Birmingham, with Prof. J. W. the Institute of Material Science in the Center of Nuclear Science in Juelich, Mays (1995−1996). Since 1998, he has been a Lecturer at the Industrial Germany, with Prof. Dr. Dieter Richter (1994−1995), and University of Chemistry Laboratory, Department of Chemistry, University of Athens. Alabama at Birmingham, with Prof. Jimmy Mays (August 1997−February He has been a Visiting Scientist at the University of Milano, Italy (March 1998). He has been a Research Associate at the University of Athens 1991); University of Alabama at Birmingham (September−October 1993); since 1998. He has published 30 papers in refereed scientific journals Max Plank Institute for Polymer Science, Germany (August 1994); National and made 27 announcements at international scientific conferences. Institute for Standards and Technology (December 1995); and IBM Almaden Research Center (February 1995). He has published 35 papers in refereed scientific journals and made 30 announcements at international scientific conferences. Nikos Hadjichristidis received his B.Sc. from the University of Athens, Greece, in 1966, his Ph.D. from the University of Lie`ge, Belgium, in 1971, and his D.Sc. from the University of Athens, Greece in 1978. He did postdoctoral research at the University of Lie`ge with Professor V. Desreux Stergios Pispas received his B.Sc. and Ph.D. from the University of Athens, (1971−1972) and National Research Council of Canada with Dr. J. Roovers Greece, in 1989 and 1994, respectively. He did postdoctoral research at (1972−1973). His career at the University of Athens has included being the University of Alabama at Birmingham, with Prof. J. W. Mays (1994− Lecturer (1973), Assistant Professor (1982), Associate Professor (1985), 1995). He has been a Research Associate at the University of Athens Full Professor (1988), Director of Industrial Chemistry Laboratory (since since 1997 and a Visiting Researcher at the National Hellenic Research 1994), and Chairman of the Chemistry Department (1991−1995 and since Foundation of Greece since 2001. He has enjoyed being a Visiting Scientist 1999). His travels include the following:Visiting Scientist, University of Lie`ge at the following facilities: Foundation for Research and Technology, Greece (Summers 1974, 1975); Visiting Research Officer, NRC of Canada (November 1990); University of Alabama at Birmingham (August− (Summer 1976); Visiting Scientist, University of Akron, at Dr. L. Fetters’ September 1992 and September−October 1993); Max Plank Institute for Laboratory (Summers 1977 through 1982); Distinguished Visiting Scientist, Polymer Science, Germany (February 1994); University of Massachusetts NRC of Canada (1983); Visiting Professor, Exxon Research and at Amherst (July−September 1995); IBM Almaden Research Center Engineering Co., NJ (since 1984, every year for 1−2 months). His further (October 1995); Foundation for Research and Technology, Greece (July accomplishments include being President of the European Polymer 1998); and Institut de Chimie des Surfaces et Interfaces-CNRS, France Federation (1995−1996), a member of the National Advisory Research (November 2000). In 1995, he received the American Institute of Chemists Council (since 1994), President of the State Highest Chemical Board (since Foundation Award for Distinguished Postdoctoral Research. He has 1995), and Director of the Institute of “Organic and Pharmaceutical published 48 papers in refereed scientific journals and made 33 Chemistry” of the National Hellenic Research Foundation (2000−2001). announcements at international scientific conferences. He has received the Academy of Athens Award for Chemistry (1989), the Empirikion Award for Sciences (1994), and the Greek Chemists Use of Multifunctional Initiators. In this Association Award (2000). He has published more than 220 papers in method, multifunctional organometallic compounds refereed scientific journals. that are capable of simultaneously initiating the polymerization of several branches are used in order equally reactive and have the same rate of initiation. to form a star polymer. There are several require- Furthermore, the initiation rate must be higher than ments that a multifunctional initiator has to fulfill the propagation rate. Only a few multifunctional in order to produce star polymers with uniform arms, initiators satisfy these requirements, and conse- low molecular weight distribution, and controllable quently, this method is not very successful. Compli- molecular weights. All the initiation sites must be cations often arise from the insolubility of these Complex Polymers by Living Anionic Polymerization Chemical Reviews, 2001, Vol. 101, No. 12 3749 initiators, due to the strong aggregation effects. The high dilution to obtain a stable microgel suspension. steric hindrance effects, caused by the high segment These microgels, which were covered by living anionic density, causes excluded volume effects. sites, were subsequently used as multifunctional Use of Multifunctional Linking Agents. This initiators to polymerize styrene, isoprene, or buta- method involves the synthesis of living macroanionic diene. A slight variation was adopted by Funke.17,18 chains and their subsequent reaction with a multi- The polymerization of DVB was initiated by living functional electrophile, which acts as the linking poly(tert-butylstyryl)lithium chains having low mo- agent. It is the most efficient way to synthesize well- lecular weights in order to avoid the solubility defined star polymers, because there can be absolute problems arising from the strong association of the control in all the synthetic steps. The functionality carbon-lithium functions in the nonpolar solvent. of the linking agent determines the number of the Rempp et al. synthesized poly(tert-butyl acrylate)16 branches of the star polymer, provided that the (PtBuA) and
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