Dendritic and Hyperbranched Polymers from Macromolecular Units: Elegant Approaches to the Synthesis of Functional Polymers

This perspective presents the state-of-the-art techniques to synthesize highly branched polymers such as dendrimers and hyperbranched polymers with well-defined linear chains between branch points. These highly branched polymers are essentially the long-chain analogues of conventional dendrimers and hyperbranched polymers and have been given many names, including dendrimer-like, DendriMac, HyperMac, etc. We cover the various synthetic strategies: the direction of synthesis (i.e., core outward or periphery inward) and the building of hyperbranched polymer either through iterative chain growth/branching reactions or from well-defined and reactive building blocks. The first section of this paper focuses on the iterative chain growth/branching reactions. These reactions have been used to create long-chain analogues of dendrimers. The second section highlights the modular synthesis of long-chain analogues of dendrimers following traditional dendrimer chemistry, based on divergent or convergent synthesis, and u...

[1]  Zhongfan Jia,et al.  Modulating Two Copper(I)-Catalyzed Orthogonal “Click” Reactions for the One-Pot Synthesis of Highly Branched Polymer Architectures at 25 °C , 2011 .

[2]  Zhongfan Jia,et al.  Directing the pathway of orthogonal 'click' reactions by modulating copper-catalytic activity. , 2011, Chemical communications.

[3]  T. Schmidt,et al.  Luminescent hyperbranched polymers : combining thiol-yne chemistry with gold-mediated C-H bond activation , 2011 .

[4]  Yezi You,et al.  An Easy Method To Convert the Topologies of Macromolecules after Polymerization , 2011 .

[5]  S. Perrier,et al.  Hyperbranched alternating block copolymers using thiol-yne chemistry: materials with tuneable properties. , 2011, Chemical communications.

[6]  S. Rimmer,et al.  Hyper/highly-branched polymers by radical polymerisations , 2010 .

[7]  S. Perrier,et al.  'Green' reversible addition-fragmentation chain-transfer (RAFT) polymerization. , 2010, Nature chemistry.

[8]  S. Perrier,et al.  The structure of randomly branched polymers synthesized by living radical methods , 2010 .

[9]  C. Hawker,et al.  Pushing the Limits for Thiol-Ene and CuAAC Reactions: Synthesis of a 6th Generation Dendrimer in a Single Day , 2010 .

[10]  S. Perrier,et al.  Describing the Structure of a Randomly Hyperbranched Polymer , 2010 .

[11]  K. Sugiyama,et al.  Combining living anionic polymerization with branching reactions in an iterative fashion to design branched polymers. , 2010, Macromolecular rapid communications.

[12]  M. Monteiro,et al.  Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr , 2010 .

[13]  Jonathan M. Dodds,et al.  HyperMacs – Highly Branched Network Precursors or Semi-Interpenetrating Networks? , 2010 .

[14]  A. Albertsson,et al.  Enhanced Electrical Conductivity by Macromolecular Architecture: Hyperbranched Electroactive and Degradable Block Copolymers Based on Poly(ε-caprolactone) and Aniline Pentamer , 2010 .

[15]  A. Kakkar,et al.  "Click" methodologies: efficient, simple and greener routes to design dendrimers. , 2010, Chemical Society reviews.

[16]  Lei Tao,et al.  Combining Thio−Bromo “Click” Chemistry and RAFT Polymerization: A Powerful Tool for Preparing Functionalized Multiblock and Hyperbranched Polymers , 2010 .

[17]  Brian S. Hawkett,et al.  Chain Transfer to Polymer and Branching in Controlled Radical Polymerizations of n-Butyl Acrylate. , 2009, Macromolecular rapid communications.

[18]  S. Perrier,et al.  Hyperbranched polymers by thiol-yne chemistry: from small molecules to functional polymers. , 2009, Journal of the American Chemical Society.

[19]  Jonathan M. Dodds,et al.  HyperMacs to HyperBlocks: A Novel Class of Branched Thermoplastic Elastomer , 2009 .

[20]  S. Aoshima,et al.  A renaissance in living cationic polymerization. , 2009, Chemical reviews.

[21]  Albena Lederer,et al.  Hyperbranched and highly branched polymer architectures--synthetic strategies and major characterization aspects. , 2009, Chemical reviews.

[22]  M. Monteiro,et al.  Rapid, Selective, and Reversible Nitroxide Radical Coupling (NRC) Reactions at Ambient Temperature , 2009 .

[23]  Xiaolan Luo,et al.  Synthesis of Dendrimer-Like Copolymers Based on the Star (Polystyrene-Poly(ethylene oxide)-Poly(ethoxyethyl glycidyl ether)) Terpolymers by Click Chemistry , 2009 .

[24]  E. Chaikof,et al.  Fast Access to Dendrimer-like Poly(ethylene oxide)s through Anionic Ring-Opening Polymerization of Ethylene Oxide and Use of Nonprotected Glycidol as Branching Agent , 2009 .

[25]  Dominik Konkolewicz.  Where are the End-Groups in a Hyperbranched Polymer? , 2009 .

[26]  V. Percec,et al.  Synthesis of dendritic macromolecules through divergent iterative thio‐bromo “Click” chemistry and SET‐LRP , 2009 .

[27]  V. Percec,et al.  Synthesis of dendrimers through divergent iterative thio-bromo “Click” chemistry , 2009 .

[28]  A. Hirao,et al.  Precise Synthesis of Dendrimer-Like Star-Branched Polystyrenes and Block Copolymers Composed of Polystyrene and Poly(methyl methacrylate) Segments by an Iterative Methodology Using Living Anionic Polymerization , 2009 .

[29]  H. Frey,et al.  Ferrocenyl‐functionalized long chain branched polydienes , 2009 .

[30]  H. Klok,et al.  Synthesis of functional polymers by post-polymerization modification. , 2009, Angewandte Chemie.

[31]  S. Carlotti,et al.  Precise Synthesis and Characterization of Fourth-Generation Dendrimer-like Star-Branched Poly(methyl methacrylate)s and Block Copolymers by Iterative Methodology Based on Living Anionic Polymerization , 2009 .

[32]  N. Hadjichristidis,et al.  Linear and Nonlinear Rheology of Dendritic Star Polymers: Experiment , 2008 .

[33]  Lian R. Hutchings,et al.  DendriMacs and HyperMacs – emerging as more than just model branched polymers. , 2008 .

[34]  Junlian Huang,et al.  Preparation of star block copolymers with polystyrene‐block‐poly(ethylene oxide) as side chains on hyperbranched polyglycerol core by combination of ATRP with atom transfer nitroxide radical coupling reaction , 2008 .

[35]  Q. Fu,et al.  One‐pot synthesis of heterograft copolymers via “graft onto” by atom transfer nitroxide radical coupling chemistry , 2008 .

[36]  A. L. Demirel,et al.  Dendrimer-Like Miktoarm Star Terpolymers : A3-(B-C)3via Click Reaction Strategy , 2008 .

[37]  M. Gauthier,et al.  Large-scale synthesis of arborescent polystyrenes , 2008 .

[38]  E. Chaikof,et al.  Janus-type dendrimer-like poly(ethylene oxide)s. , 2008, Journal of the American Chemical Society.

[39]  D. Vlassopoulos,et al.  Viscoelastic and Dielectric Relaxation of a Cayley-Tree-Type Polyisoprene: Test of Molecular Picture of Dynamic Tube Dilation , 2008 .

[40]  Angus A. Gray-Weale,et al.  Models for randomly hyperbranched polymers: Theory and simulation. , 2008, The Journal of chemical physics.

[41]  Lian R. Hutchings,et al.  A Facile Route to Synthesize Well‐Defined Polybutadiene DendriMacs , 2008 .

[42]  Takumi Watanabe,et al.  Synthesis and AFM structural imaging of dendrimer-like star-branched polystyrenes. , 2008, Journal of the American Chemical Society.

[43]  Carl N. Urbani,et al.  Divergent Synthesis and Self-Assembly of Amphiphilic Polymeric Dendrons with Selective Degradable Linkages , 2008 .

[44]  Lian R. Hutchings,et al.  HyperMacs – long chain hyperbranched polymers : a dramatically improved synthesis and qualitative rheological analysis. , 2008 .

[45]  Craig A. Bell,et al.  Convergent Synthesis of Second Generation AB-Type Miktoarm Dendrimers Using ``Click'' Chemistry Catalyzed by Copper Wire , 2008 .

[46]  C. Pan,et al.  Preparation of dendrimer-like copolymers based on polystyrene and poly(l-lactide) and formation of hollow microspheres , 2008 .

[47]  Y. Gnanou,et al.  Combination of an anionic terminator multifunctional initiator and divergent carbanionic polymerization: application to the synthesis of dendrimer-like polymers and of asymmetric and miktoarm stars. , 2008, Journal of the American Chemical Society.

[48]  Lian R. Hutchings,et al.  Rheological properties of HyperMacs—long‐chain branched analogues of hyperbranched polymers , 2007 .

[49]  Carl N. Urbani,et al.  Reactive Alkyne and Azide Solid Supports To Increase Purity of Novel Polymeric Stars and Dendrimers via the “Click” Reaction , 2007 .

[50]  Nikos Hadjichristidis,et al.  Entangled Dendritic Polymers and Beyond: Rheology of Symmetric Cayley-Tree Polymers and Macromolecular Self-Assemblies , 2007 .

[51]  E. Chaikof,et al.  Bouquet-type dendrimerlike poly(ethylene oxide)s with a focal aldehyde and peripheral hydroxyls. , 2007, Biomacromolecules.

[52]  D. Taton,et al.  Dendrimer-like polymers: a new class of structurally precise dendrimers with macromolecular generations , 2007 .

[53]  J. Hedrick,et al.  A distinctive organocatalytic approach to complex macromolecular architectures. , 2007, Angewandte Chemie.

[54]  Angus A. Gray-Weale,et al.  Randomly hyperbranched polymers. , 2007, Physical review letters.

[55]  C. Pan,et al.  Thermal control over the topology of cleavable polymers: from linear to hyperbranched structures. , 2007, Journal of the American Chemical Society.

[56]  Holger Frey,et al.  A Facile Two‐Step Route to Branched Polyisoprenes via ABn‐Macromonomers , 2007 .

[57]  S. Kwak,et al.  Influence of hyperbranched against linear architecture on crystallization behavior of poly(ε-caprolactone)s in binary blends with poly(vinyl chloride) , 2007 .

[58]  D. Taton,et al.  Polystyrene-b-poly(tert-butyl acrylate) and polystyrene-b-poly(acrylic acid) dendrimer-like copolymers: two-dimensional self-assembly at the air-water interface. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[59]  Kenji Sugiyama,et al.  Precise synthesis of well‐defined dendrimer‐like star‐branched polymers by iterative methodology based on living anionic polymerization , 2006 .

[60]  S. Hou,et al.  Controlled polymerizations as tools for the design of star‐like and dendrimer‐like polymers , 2006 .

[61]  Yves Gnanou,et al.  pH responsiveness of dendrimer-like poly(ethylene oxide)s. , 2006, Journal of the American Chemical Society.

[62]  Michael J Monteiro,et al.  Synthesis of 3-miktoarm stars and 1st generation mikto dendritic copolymers by "living" radical polymerization and "click" chemistry. , 2006, Journal of the American Chemical Society.

[63]  K. Sugiyama,et al.  Synthesis of Dendrimer-Like Star-Branched Poly(methyl methacrylate)s of Generations Consisting of Four Branched Polymer Chains at Each Junction by Iterative Methodology Involving Coupling and Transformation Reactions , 2006 .

[64]  C. Pan,et al.  Synthesis and characterizations of well-defined dendrimer-like copolymers with the second and third generation based on polystyrene and poly(l-lactide) , 2006 .

[65]  L. R. Hutchings,et al.  HyperMacs. Long Chain Branched Analogues of Hyperbranched Polymers Prepared by the Polycondensation of AB2 Macromonomers , 2006 .

[66]  K. Sugiyama,et al.  Precise synthesis of dendron-like hyperbranched polymers and block copolymers by an iterative approach involving living anionic polymerization, coupling reaction, and transformation reaction , 2006 .

[67]  Nikos Hadjichristidis,et al.  Synthesis of Well-Defined Second (G-2) and Third (G-3) Generation Dendritic Polybutadienes , 2006 .

[68]  Lian R. Hutchings,et al.  DendriMacs. Well-Defined Dendritically Branched Polymers Synthesized by an Iterative Convergent Strategy Involving the Coupling Reaction of AB2 Macromonomers , 2006 .

[69]  You Han Bae,et al.  Polymer Architecture and Drug Delivery , 2006, Pharmaceutical Research.

[70]  J. V. van Hest,et al.  Modular synthesis of block copolymers via cycloaddition of terminal azide and alkyne functionalized polymers. , 2005, Chemical communications.

[71]  Sébastien Perrier,et al.  Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization , 2005 .

[72]  D. Taton,et al.  MALDI-TOF analysis of dendrimer-like poly(ethylene oxide)s , 2005 .

[73]  T. Bera,et al.  Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator , 2005 .

[74]  Takumi Watanabe,et al.  Precise Synthesis of Dendrimer-like Star-Branched Poly(methyl methacrylate)s up to Seventh Generation by an Iterative Divergent Approach Involving Coupling and Transformation Reactions , 2005 .

[75]  J. Esko,et al.  Dendrimer-like PEO glycopolymers exhibit anti-inflammatory properties. , 2005, Journal of the American Chemical Society.

[76]  E. Chaikof,et al.  Toward an easy access to dendrimer-like poly(ethylene oxide)s. , 2005, Journal of the American Chemical Society.

[77]  G. Moad,et al.  Living radical polymerization by the RAFT process , 2005 .

[78]  Lian R. Hutchings,et al.  HyperMacs: Highly Branched Polymers Prepared by the Polycondensation of AB2 Macromonomers, Synthesis and Characterization , 2005 .

[79]  D. Taton,et al.  Synthesis and Investigation of Surface Properties of Dendrimer-like Copolymers Based on Polystyrene and Poly(tert-butylacrylate) , 2005 .

[80]  C. Hawker,et al.  Structurally diverse dendritic libraries : A highly efficient functionalization approach using Click chemistry , 2005 .

[81]  Yves Gnanou,et al.  Synthesis of Dendrimer-Like Polystyrene by Atom Transfer Radical Polymerization and Investigation of Their Viscosity Behavior , 2005 .

[82]  S. Perrier,et al.  One-Pot Hyperbranched Polymer Synthesis Mediated by Reversible Addition Fragmentation Chain Transfer (RAFT) Polymerization , 2005 .

[83]  K. Sugiyama,et al.  Precise syntheses of chain-multi-functionalized polymers, star-branched polymers, star-linear block polymers, densely branched polymers, and dendritic branched polymers based on iterative approach using functionalized 1,1-diphenylethylene derivatives , 2005 .

[84]  S. Kwak,et al.  Concentration fluctuation and cooperative chain mobility of hyperbranched poly(ε-caprolactone)s investigated by photon correlation spectroscopy , 2004 .

[85]  D. Lewis,et al.  Polymer architectures via reversible addition fragmentation chain transfer (RAFT) polymerization , 2004 .

[86]  A. Matsuo,et al.  Synthesis of Well-Defined Dendrimer-like Branched Polymers and Block Copolymer by the Iterative Approach Involving Coupling Reaction of Living Anionic Polymer and Functionalization , 2004 .

[87]  M. Ballauff,et al.  Dendrimers in solution: insight from theory and simulation. , 2004, Angewandte Chemie.

[88]  S. Kwak,et al.  Architectural Effects of Poly(ε-caprolactone)s on the Crystallization Kinetics , 2004 .

[89]  Mario Gauthier,et al.  Dendrigraft polymers: macromolecular engineering on a mesoscopic scale , 2004 .

[90]  V. Percec,et al.  Toward self‐assembling dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible terminator multifunctional initiator , 2004 .

[91]  M. Gauthier,et al.  Synthesis of arborescent polystyrene-graft-polyisoprene copolymers using acetylated substrates , 2004 .

[92]  Leonie Barner,et al.  Complex Molecular Architecture Polymers via RAFT , 2004 .

[93]  S. Kwak,et al.  Synthesis and Characterization of Hyperbranched Poly(∊-caprolactone)s Having Different Lengths of Homologous Backbone Segments , 2003 .

[94]  D. Taton,et al.  Synthesis and Surface Properties of Amphiphilic Star-Shaped and Dendrimer-like Copolymers Based on Polystyrene Core and Poly(ethylene oxide) Corona , 2003 .

[95]  Steve P. Rannard,et al.  Dendrimers: a new class of nanoscopic containers and delivery devices , 2003 .

[96]  E. Chaikof,et al.  Synthesis of functionalized multiarm poly(ethylene oxide) stars , 2003 .

[97]  Pascal Viville,et al.  Synthesis and Characterization of Water-Soluble Amphipatic Polystyrene-Based Dendrigrafts , 2003 .

[98]  J. Hedrick,et al.  Impact of Core Architecture on Solution Properties of Dendrimer-like Star Copolymers , 2003 .

[99]  E. Chaikof,et al.  Synthesis of Water-Soluble Star-Block and Dendrimer-like Copolymers Based on Poly(ethylene oxide) and Poly(acrylic acid) , 2003 .

[100]  T. Bera,et al.  Universal iterative strategy for the divergent synthesis of dendritic macromolecules from conventional monomers by a combination of living radical polymerization and irreversible TERminator multifunctional INItiator (TERMINI). , 2003, Journal of the American Chemical Society.

[101]  J. Bernard,et al.  Functional Polystyrene Combs and Dendrigrafts, 1 , 2003 .

[102]  J. Hedrick,et al.  Structural properties of star-like dendrimers in solution , 2002 .

[103]  V. Urban,et al.  Dynamics of star-burst dendrimers in solution in relation to their structural properties , 2002 .

[104]  Nikos Hadjichristidis,et al.  Synthesis of well‐defined second‐generation dendritic polymers of isoprene (I) and styrene (S): (S2I)3, (SI′I)3, (I″I′I)3, and (I′2I)4 , 2002 .

[105]  M. Pitsikalis,et al.  Polymers with complex architecture by living anionic polymerization. , 2001, Chemical reviews.

[106]  E. Harth,et al.  New polymer synthesis by nitroxide mediated living radical polymerizations. , 2001, Chemical reviews.

[107]  Daniel M. Knauss,et al.  Graft copolymers from star‐shaped and hyperbranched polystyrene macromonomers , 2001 .

[108]  Mitsutoshi Jikei,et al.  Hyperbranched polymers: a promising new class of materials , 2001 .

[109]  Zainuddin Muchtar,et al.  HYPERBRANCHED NANOMOLECULES: REGULAR POLYSTYRENE DENDRIGRAFTS , 2001 .

[110]  D. Taton,et al.  Stars and dendrimer‐like architectures by the divergent method using controlled radical polymerization , 2001 .

[111]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[112]  J. Hedrick,et al.  Constitutional Isomers of Dendrimer-like Star Polymers: Design, Synthesis, and Conformational and Structural Properties , 2000 .

[113]  Yves Gnanou,et al.  Amphiphilic Stars and Dendrimer-Like Architectures Based on Poly(Ethylene Oxide) and Polystyrene , 2000 .

[114]  D. Sherrington,et al.  Facile, versatile and cost effective route to branched vinyl polymers , 2000 .

[115]  J. Hedrick,et al.  Transport properties of hyperbranched and dendrimer-like star polymers , 2000 .

[116]  J. Hedrick,et al.  Highly Branched Block Copolymers: Design, Synthesis, and Morphology , 1999 .

[117]  R. Mülhaupt,et al.  Controlled Synthesis of Hyperbranched Polyglycerols by Ring-Opening Multibranching Polymerization , 1999 .

[118]  J. Hedrick,et al.  Layered Dendritic Block Copolymers. , 1998, Angewandte Chemie.

[119]  J. Hedrick,et al.  Dendrimer-like star block and amphiphilic copolymers by combination of ring opening and atom transfer radical polymerization , 1998 .

[120]  J. Hedrick,et al.  Highly branched radial block copolymers via dendritic initiation of aliphatic polyesters , 1998 .

[121]  J. Chiefari,et al.  Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process , 1998 .

[122]  J. Hedrick,et al.  Dendrimer-like Star Polymers , 1998 .

[123]  Holger Frey,et al.  Degree of branching in hyperbranched polymers , 1997 .

[124]  Jean M. J. Fréchet,et al.  Dendrimers and Hyperbranched Polymers: Two Families of Three-Dimensional Macromolecules with Similar but Clearly Distinct Properties , 1996 .

[125]  M. Sawamoto,et al.  Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization , 1995 .

[126]  R. B. Grubbs,et al.  Self-Condensing Vinyl Polymerization: An Approach to Dendritic Materials , 1995, Science.

[127]  Y. Gnanou,et al.  From star‐shaped to dendritic poly(ethylene oxide)s: Toward increasingly branched architectures by anionic polymerization , 1995 .

[128]  Krzysztof Matyjaszewski,et al.  Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes , 1995 .

[129]  Gordon K. Hamer,et al.  Narrow molecular weight resins by a free-radical polymerization process , 1993 .

[130]  Jean M. J. Fréchet,et al.  Unique behavior of dendritic macromolecules: intrinsic viscosity of polyether dendrimers , 1992 .

[131]  Jean M. J. Fréchet,et al.  One-step synthesis of hyperbranched dendritic polyesters , 1991 .

[132]  O. Webster.  Living Polymerization Methods , 1991, Science.

[133]  George R. Newkome,et al.  Micelles. Part 1. Cascade molecules: a new approach to micelles. A [27]-arborol , 1985 .

[134]  James L White,et al.  Interaction of melt spinning and drawing variables on the crystalline morphology and mechanical properties of high‐density and low‐density polyethylene fiber , 1974 .

[135]  O. J. Sweeting,et al.  Polyethylene: Preparation, Structure, And Properties , 1957 .

[136]  M. Szwarc.  |[lsquo]|Living|[rsquo]| Polymers , 1956 .

[137]  Paul J. Flory,et al.  Molecular Size Distribution in Three Dimensional Polymers. VI. Branched Polymers Containing A—R—Bf-1 Type Units , 1952 .

[138]  Craig A. Bell,et al.  Self-Assembly of Amphiphilic Polymeric Dendrimers Synthesized with Selective Degradable Linkages , 2008 .

[139]  Krzysztof Matyjaszewski,et al.  Controlled/living radical polymerization: Features, developments, and perspectives , 2007 .

[140]  D. Sherrington,et al.  Branched methacrylate copolymers from multifunctional monomers: chemical composition and physical architecture distributions , 2002 .

[141]  Jean M. J. Fréchet,et al.  Molecular Ball Bearings: The Unusual Melt Viscosity Behavior of Dendritic Macromolecules , 1995 .

[142]  M. Sawamoto.  Modern cationic vinyl polymerization , 1991 .

[143]  C. Hawker,et al.  A new convergent approach to monodisperse dendritic macromolecules , 1990 .

[144]  George R. Newkome,et al.  MICELLES. PART 1. CASCADE MOLECULES: A NEW APPROACH TO MICELLES. A (27)-ARBOROL , 1985 .

[145]  James R. Dewald,et al.  A New Class of Polymers: Starburst-Dendritic Macromolecules , 1985 .