Block Copolymers: Synthesis, Self-Assembly, and Applications

Research on block copolymers (BCPs) has played a critical role in the development of polymer chemistry, with numerous pivotal contributions that have advanced our ability to prepare, characterize, theoretically model, and technologically exploit this class of materials in a myriad of ways in the fields of chemistry, physics, material sciences, and biological and medical sciences. The breathtaking progress has been driven by the advancement in experimental techniques enabling the synthesis and characterization of a wide range of block copolymers with tailored composition, architectures, and properties. In this review, we briefly discussed the recent progress in BCP synthesis, followed by a discussion of the fundamentals of self-assembly of BCPs along with their applications.

[1]  N. Terrill,et al.  Morphologies of microphase-separated A2B simple graft copolymers , 1996 .

[2]  J. Mays,et al.  Macromolecular Architectures by Living and Controlled/Living Polymerizations , 2006 .

[3]  C. Grant Willson,et al.  Block Copolymer Lithography , 2014 .

[4]  E. Thomas,et al.  Impact of Morphological Orientation in Determining Mechanical Properties in Triblock Copolymer Systems , 1996 .

[5]  Marc A. Hillmyer,et al.  Polylactide-poly(dimethylsiloxane)-polylactide triblock copolymers as multifunctional materials for nanolithographic applications. , 2010, ACS nano.

[6]  Bradley F. Chmelka,et al.  Generalized syntheses of large-pore mesoporous metal oxides with semicrystalline frameworks , 1998, Nature.

[7]  Krzysztof Matyjaszewski,et al.  ATRP in the design of functional materials for biomedical applications. , 2012, Progress in polymer science.

[8]  D. Taton,et al.  Controlled/living radical polymerization , 2014 .

[9]  Frank S. Bates,et al.  Origins of Complex Self-Assembly in Block Copolymers , 1996 .

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

[11]  Jamie M. Messman,et al.  Tunable morphologies from charged block copolymers , 2010 .

[12]  Graeme Moad,et al.  A more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization : The RAFT process , 1999 .

[13]  V. Bocharova,et al.  A star-shaped single lithium-ion conducting copolymer by grafting a POSS nanoparticle , 2017 .

[14]  J. Mays,et al.  Design and Synthesis of Multigraft Copolymer Thermoplastic Elastomers: Superelastomers , 2018 .

[15]  K. Matyjaszewski,et al.  ARGET ATRP of methyl methacrylate in the presence of nitrogen‐based ligands as reducing agents , 2009 .

[16]  Dennis E Discher,et al.  Self-porating polymersomes of PEG-PLA and PEG-PCL: hydrolysis-triggered controlled release vesicles. , 2004, Journal of controlled release : official journal of the Controlled Release Society.

[17]  L. Fetters,et al.  Synthesis and Properties of Block Copolymers. 4. Poly(p-tert-butylstyrene-diene-p-tert-butylstyrene) and Poly(p-tert-butylstyrene-isoprene-styrene) , 1977 .

[18]  R. Advíncula,et al.  Polymer brushes by living anionic surface initiated polymerization on flat silicon (SiOx) and gold surfaces: Homopolymers and block copolymers , 2002 .

[19]  Wenping Wang,et al.  Preparation and Characterization of Thermally Responsive and Biodegradable Block Copolymer Comprised of PNIPAAM and PLA by Combination of ROP and RAFT Methods , 2004 .

[20]  C. Barner‐Kowollik,et al.  Reversible Addition Fragmentation Chain Transfer (RAFT) and Hetero-Diels−Alder Chemistry as a Convenient Conjugation Tool for Access to Complex Macromolecular Designs , 2008 .

[21]  A. Eisenberg,et al.  Multiple Morphologies and Characteristics of “Crew-Cut” Micelle-like Aggregates of Polystyrene-b-poly(acrylic acid) Diblock Copolymers in Aqueous Solutions , 1996 .

[22]  S. Honda,et al.  Topology-directed control on thermal stability: micelles formed from linear and cyclized amphiphilic block copolymers. , 2010, Journal of the American Chemical Society.

[23]  D. Gigmes,et al.  3.10 - Nitroxide-Mediated Polymerization , 2012 .

[24]  M. Szwarc,et al.  POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS1 , 1956 .

[25]  A. Sokolov,et al.  Gas separation mechanism of CO2 selective amidoxime-poly(1-trimethylsilyl-1-propyne) membranes , 2017 .

[26]  Ying Wan,et al.  On the controllable soft-templating approach to mesoporous silicates. , 2007, Chemical reviews.

[27]  J. Mays,et al.  Experimental techniques in high‐vacuum anionic polymerization , 2005 .

[28]  F. Bates,et al.  Polymer-Polymer Phase Behavior , 1991, Science.

[29]  Krzysztof Matyjaszewski,et al.  Preparation of homopolymers and block copolymers in miniemulsion by ATRP using activators generated by electron transfer (AGET). , 2005, Journal of the American Chemical Society.

[30]  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 .

[31]  D. Zhao,et al.  Controlled Synthesis and Functionalization of Ordered Large‐Pore Mesoporous Carbons , 2010 .

[32]  B. Sumerlin,et al.  New directions in thermoresponsive polymers. , 2013, Chemical Society reviews.

[33]  S. Armes,et al.  Synthesis of Biomimetic Poly(2-(methacryloyloxy)ethyl phosphorylcholine) Nanolatexes via Atom Transfer Radical Dispersion Polymerization in Alcohol/Water Mixtures , 2010 .

[34]  Easan Sivaniah,et al.  SAXS Analysis of the Order−Disorder Transition and the Interaction Parameter of Polystyrene-block-poly(methyl methacrylate) , 2008 .

[35]  J. Mays,et al.  Mechanical Properties and Hysteresis Behaviour of Multigraft Copolymers , 2006 .

[36]  Sol M Gruner,et al.  Block copolymer self-assembly–directed synthesis of mesoporous gyroidal superconductors , 2016, Science Advances.

[37]  U. Wiesner,et al.  Block Copolymer Based Composition and Morphology Control in Nanostructured Hybrid Materials for Energy Conversion and Storage Solar Cells, Batteries, and Fuel Cells , 2011 .

[38]  Paschalis Alexandridis,et al.  Amphiphilic Block Copolymers: Self-Assembly and Applications , 2000 .

[39]  M. Gutiérrez,et al.  DES assisted synthesis of hierarchical nitrogen-doped carbon molecular sieves for selective CO2versus N2 adsorption , 2014 .

[40]  N. Hadjichristidis,et al.  Synthesis of Model Multigraft Copolymers of Butadiene with Randomly Placed Single and Double Polystyrene Branches , 1998 .

[41]  Doo Sung Lee,et al.  Poly(ethylene glycol)-b-poly(lysine) copolymer bearing nitroaromatics for hypoxia-sensitive drug delivery. , 2016, Acta biomaterialia.

[42]  T. Lodge,et al.  Micelle/Inverse Micelle Self-Assembly of a PEO−PNIPAm Block Copolymer in Ionic Liquids with Double Thermoresponsivity , 2010 .

[43]  D. Zhao,et al.  Solvent evaporation induced aggregating assembly approach to three-dimensional ordered mesoporous silica with ultralarge accessible mesopores. , 2011, Journal of the American Chemical Society.

[44]  T. Aida,et al.  Cyclic block copolymers for controlling feature sizes in block copolymer lithography. , 2012, ACS nano.

[45]  A. Hirao,et al.  Synthesis of well-defined functionalized polymers and star branched polymers by means of living anionic polymerization using specially designed 1,1-diphenylethylene derivatives , 2000 .

[46]  Hongda Du,et al.  Influences of Mesopore Size on Oxygen Reduction Reaction Catalysis of Pt/Carbon Aerogels , 2007 .

[47]  W. Hinsberg,et al.  Block copolymer based nanostructures: materials, processes, and applications to electronics. , 2010, Chemical reviews.

[48]  D. Zhao,et al.  New Insight into the Synthesis of Large-Pore Ordered Mesoporous Materials. , 2017, Journal of the American Chemical Society.

[49]  Nikos Hadjichristidis,et al.  Block Copolymers: Synthetic Strategies, Physical Properties, and Applications , 2002 .

[50]  L. Fetters,et al.  Synthesis and Properties of Block Polymers. I. Poly-α-methylstyrene-Polyisoprene-Poly-α-methylstyrene , 1969 .

[51]  J. Rieger,et al.  Amphiphilic block copolymers from a direct and one-pot RAFT synthesis in water. , 2011, Macromolecular rapid communications.

[52]  Shiping Zhu,et al.  Toward Well-Controlled ab Initio RAFT Emulsion Polymerization of Styrene Mediated by 2-(((Dodecylsulfanyl)carbonothioyl)sulfanyl)propanoic Acid , 2011 .

[53]  Guolin Lu,et al.  Double-bond-containing polyallene-based triblock copolymers via phenoxyallene and (meth)acrylate , 2017, Scientific Reports.

[54]  K. Matyjaszewski,et al.  Progress in controlled radical polymerization : mechanisms and techniques , 2012 .

[55]  Hua Wei,et al.  Thermo-sensitive polymeric micelles based on poly(N-isopropylacrylamide) as drug carriers , 2009 .

[56]  Soojin Park,et al.  Macroscopic 10-Terabit–per–Square-Inch Arrays from Block Copolymers with Lateral Order , 2009, Science.

[57]  Craig J Hawker,et al.  Cross-linked block copolymer micelles: functional nanostructures of great potential and versatility. , 2006, Chemical Society reviews.

[58]  T. Lodge,et al.  High-modulus, high-conductivity nanostructured polymer electrolyte membranes via polymerization-induced phase separation. , 2014, Nano letters.

[59]  Frank S Bates,et al.  On the Origins of Morphological Complexity in Block Copolymer Surfactants , 2003, Science.

[60]  H. Klok,et al.  Advanced drug delivery devices via self-assembly of amphiphilic block copolymers. , 2001, Advanced drug delivery reviews.

[61]  Daniel J. Keddie,et al.  A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization. , 2014, Chemical Society reviews.

[62]  Eun Hye Kim,et al.  Microdomain Orientation of PS-b-PMMA by Controlled Interfacial Interactions , 2008 .

[63]  Erin M. Lennon,et al.  Free energy evaluation in field-theoretic polymer simulations. , 2008, Physical review letters.

[64]  P. Théato Controlled and Living Polymerizations: From Mechanisms to Applications , 2010 .

[65]  M. Tadé,et al.  Synthesis of nitrogen-doped mesoporous carbon spheres with extra-large pores through assembly of diblock copolymer micelles. , 2014, Angewandte Chemie.

[66]  H. Yamashita,et al.  Enhanced photocatalytic properties of TiO2-loaded porous silica with hierarchical macroporous and mesoporous architectures in water purification , 2015 .

[67]  Takuya Yamamoto,et al.  Topological polymer chemistry: a cyclic approach toward novel polymer properties and functions , 2011 .

[68]  Jin Kon Kim,et al.  Functional nanomaterials based on block copolymer self-assembly , 2010 .

[69]  F. Bates,et al.  Aqueous Dispersions of Poly(ethylene oxide)-b-poly(γ-methyl-ε-caprolactone) Block Copolymers , 2006 .

[70]  Sheng Dai,et al.  Carbon Materials for Chemical Capacitive Energy Storage , 2012 .

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

[72]  R. Advíncula,et al.  Living Anionic Surface Initiated Polymerization (SIP) of Styrene from Clay Surfaces , 2001 .

[73]  J. Mays,et al.  Living anionic polymerization , 1999 .

[74]  Jing Wei,et al.  A Controllable Synthesis of Rich Nitrogen‐Doped Ordered Mesoporous Carbon for CO2 Capture and Supercapacitors , 2013 .

[75]  Craig J. Hawker,et al.  Interfacial Segregation in Disordered Block Copolymers: Effect of Tunable Surface Potentials , 1997 .

[76]  M. Ouchi,et al.  Nitroxide-Mediated Polymerization , 2012 .

[77]  R. Segalman,et al.  Structure–Conductivity Relationships of Block Copolymer Membranes Based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing , 2016 .

[78]  Craig J. Hawker,et al.  The Convergence of Synthetic Organic and Polymer Chemistries , 2005, Science.

[79]  M. Beiner,et al.  High temperature thermoplastic elastomers synthesized by living anionic polymerization in hydrocarbon solvent at room temperature , 2016 .

[80]  J. Pople,et al.  Morphology and thermodynamic properties of a copolymer with an electronically conducting block: poly(3-ethylhexylthiophene)-block-poly(ethylene oxide). , 2012, Nano letters.

[81]  J. Bennett,et al.  Industrial applications , 2007, DATE.

[82]  Schick,et al.  Stable and unstable phases of a diblock copolymer melt. , 1994, Physical review letters.

[83]  V. Bocharova,et al.  Effect of Chain Rigidity on the Decoupling of Ion Motion from Segmental Relaxation in Polymerized Ionic Liquids: Ambient and Elevated Pressure Studies , 2017 .

[84]  D. Hammer,et al.  Cross-linked polymersome membranes: Vesicles with broadly adjustable properties , 2002 .

[85]  M. Schick,et al.  Self-assembly of block copolymers , 1996 .

[86]  Xiangfang Peng,et al.  Poly(vinylidene fluoride) derived fluorine-doped magnetic carbon nanoadsorbents for enhanced chromium removal , 2017 .

[87]  Lei Wan,et al.  Topcoat Approaches for Directed Self-Assembly of Strongly Segregating Block Copolymer Thin Films , 2013 .

[88]  Block Copolymer Domain Reorientation in an Electric Field: An in-Situ Small-Angle X-ray Scattering Study , 2004 .

[89]  J. Mays,et al.  Nonlinear Block Copolymer Architectures , 1998 .

[90]  R. Sheldon Living Polymers , 1969, Nature.

[91]  K. Dorfman,et al.  Thermal processing of diblock copolymer melts mimics metallurgy , 2017, Science.

[92]  Lei Liu,et al.  Direct synthesis of ordered mesoporous carbons. , 2013, Chemical Society reviews.

[93]  S. Lecommandoux,et al.  On the physics of block copolymers , 2006 .

[94]  N. Hadjichristidis,et al.  Heterofunctional Linking Agents for the Synthesis of Well-Defined Block Copolymers of Dimethylsiloxane and tert-Butyl Methacrylate or 2-Vinylpyridine , 2001 .

[95]  K. Matyjaszewski,et al.  Use of Ascorbic Acid as Reducing Agent for Synthesis of Well-Defined Polymers by ARGET ATRP , 2007 .

[96]  Brian G. Trewyn,et al.  Mesoporous Silica Nanoparticles for Drug Delivery and Biosensing Applications , 2007 .

[97]  Xiaoqin Yan,et al.  Ordered nanoporous silica with periodic 30-60 nm pores as an effective support for gold nanoparticle catalysts with enhanced lifetime. , 2010, Journal of the American Chemical Society.

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

[99]  C. Brinker,et al.  Syntheses of Silica/Polystyrene-block-Poly(ethylene oxide) Films with Regular and Reverse Mesostructures of Large Characteristic Length Scales by Solvent Evaporation-Induced Self-Assembly , 2001 .

[100]  Debra R Rolison,et al.  Catalytic Nanoarchitectures--the Importance of Nothing and the Unimportance of Periodicity , 2003, Science.

[101]  I. Hamley Nanostructure fabrication using block copolymers , 2003 .

[102]  Jiahua Zhu,et al.  All acrylic-based thermoplastic elastomers with high upper service temperature and superior mechanical properties , 2017 .

[103]  Fenghua Meng,et al.  Biodegradable polymersomes as a basis for artificial cells: encapsulation, release and targeting. , 2005, Journal of controlled release : official journal of the Controlled Release Society.

[104]  K. Matyjaszewski,et al.  "Living"/Controlled Radical Polymerization. Transition-Metal-Catalyzed Atom Transfer Radical Polymerization in the Presence of a Conventional Radical Initiator , 1995 .

[105]  Rina Maeda,et al.  Perpendicularly oriented sub-10-nm block copolymer lamellae by atmospheric thermal annealing for one minute , 2016, Scientific Reports.

[106]  Wei Lu,et al.  Preparation and brain delivery property of biodegradable polymersomes conjugated with OX26. , 2008, Journal of controlled release : official journal of the Controlled Release Society.

[107]  K. Matyjaszewski,et al.  Facile Arm-First Synthesis of Star Block Copolymers via ARGET ATRP with ppm Amounts of Catalyst , 2016 .

[108]  A. Hirao,et al.  Recent advance in living anionic polymerization of functionalized styrene derivatives , 2002 .

[109]  J. Mays,et al.  Morphology and tensile properties of multigraft copolymers with regularly spaced tri-, tetra-, and hexafunctional junction points , 2006 .

[110]  D. Zhao,et al.  Large-pore ordered mesoporous materials templated from non-Pluronic amphiphilic block copolymers. , 2013, Chemical Society reviews.

[111]  D. Zhao,et al.  Ordered mesoporous silicas and carbons with large accessible pores templated from amphiphilic diblock copolymer poly(ethylene oxide)-b-polystyrene. , 2007, Journal of the American Chemical Society.

[112]  Mitchell A. Winnik,et al.  Cylindrical Block Copolymer Micelles and Co-Micelles of Controlled Length and Architecture , 2007, Science.

[113]  Weiyu Wang Novel Thermoplastic Elastomers based on Benzofulvene: Synthesis and Mechanical Properties , 2015 .

[114]  F. Bates,et al.  Influence of Conformational Asymmetry on Polymer−Polymer Interactions: An Entropic or Enthalpic Effect? , 2002 .

[115]  S. Förster,et al.  From self-organizing polymers to nanohybrid and biomaterials. , 2002, Angewandte Chemie.

[116]  D. Zhao,et al.  Design of Amphiphilic ABC Triblock Copolymer for Templating Synthesis of Large-Pore Ordered Mesoporous Carbons with Tunable Pore Wall Thickness , 2009 .

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

[118]  U. Schubert,et al.  Supramolecular engineering with macromolecules: an alternative concept for block copolymers. , 2002, Angewandte Chemie.

[119]  Hongwei Zhang,et al.  Synthesis of Block Copolymers of Styrene and Methyl Methacrylate by Conventional Free Radical Polymerization in Room Temperature Ionic Liquids , 2002 .

[120]  Y. Yagcı,et al.  Block copolymer synthesis in one shot: concurrent metal-free ATRP and ROP processes under sunlight , 2017 .

[121]  E. Harth,et al.  Accurate Structural Control and Block Formation in the Living Polymerization of 1,3-Dienes by Nitroxide-Mediated Procedures , 2000 .

[122]  T. Hoye,et al.  Sustainable Thermoplastic Elastomers from Terpene-Derived Monomers. , 2014, ACS macro letters.

[123]  G. Fredrickson,et al.  Block Copolymers—Designer Soft Materials , 1999 .

[124]  K. Winey,et al.  Transport Properties of Sulfonated Poly(styrene-b-isobutylene-b-styrene) Triblock Copolymers at High Ion-Exchange Capacities , 2006 .

[125]  Andreas Stein,et al.  Porous Electrode Materials for Lithium‐Ion Batteries – How to Prepare Them and What Makes Them Special , 2012 .

[126]  N. Hadjichristidis,et al.  Synthesis of model linear tetrablock quaterpolymers and pentablock quintopolymers of ethylene oxide , 2002 .

[127]  T. Kyotani,et al.  Templated Nanocarbons for Energy Storage , 2012, Advanced materials.

[128]  J. Mays,et al.  Synthesis of combs, centipedes, and barbwires: Poly(isoprene-graft-styrene) regular multigraft copolymers with trifunctional, tetrafunctional, and hexafunctional branch points , 2002 .

[129]  Qiuyu Zhang,et al.  Synthesis and Characterization of Graft Copolymers Poly(isoprene-g-styrene) of High Molecular Weight by a Combination of Anionic Polymerization and Emulsion Polymerization , 2015 .

[130]  Yuliang Yang,et al.  Discovering ordered phases of block copolymers: new results from a generic Fourier-space approach. , 2008, Physical review letters.

[131]  J. Brédas,et al.  Morphology and mechanical properties of poly(methylmethacrylate)-b-poly(alkylacrylate)-b-poly(methylmethacrylate) , 2001 .

[132]  V. Bocharova,et al.  Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies , 2017 .

[133]  A. Whittaker,et al.  Control of the orientation of symmetric poly(styrene)-block-poly(D,L-lactide) block copolymers using statistical copolymers of dissimilar composition. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[134]  S. Gruner,et al.  Morphology Diagram of a Diblock Copolymer−Aluminosilicate Nanoparticle System , 2009 .

[135]  Marc A. Hillmyer,et al.  Synthesis, Thermodynamics, and Dynamics of Poly(4-tert-butylstyrene-b-methyl methacrylate) , 2012 .

[136]  H. L. Stephens,et al.  Handbook of Elastomers , 2000 .

[137]  Christopher J. Ellison,et al.  Oligosaccharide/silicon-containing block copolymers with 5 nm features for lithographic applications. , 2012, ACS nano.

[138]  M. Jaroniec,et al.  Characterization of the Porous Structure of SBA-15 , 2000 .

[139]  Y. Yamauchi,et al.  Tailored design of functional nanoporous carbon materials toward fuel cell applications , 2014 .

[140]  Christopher J. Ellison,et al.  Polarity-Switching Top Coats Enable Orientation of Sub–10-nm Block Copolymer Domains , 2012, Science.

[141]  Shiping Zhu,et al.  Ab Initio Batch Emulsion RAFT Polymerization of Styrene Mediated by Poly(acrylic acid-b-styrene) Trithiocarbonate , 2009 .

[142]  M. Jaroniec,et al.  Molecular-based design and emerging applications of nanoporous carbon spheres. , 2015, Nature materials.

[143]  Tatsuo Kimura Colloidal templating fabrication of aluminum-organophosphonate films using high molecular weight PS-b-PEO. , 2011, Chemistry, an Asian journal.

[144]  Kunlun Hong,et al.  Synthesis of a large-scale highly ordered porous carbon film by self-assembly of block copolymers. , 2004, Angewandte Chemie.

[145]  J. Mays,et al.  Regular Comb Polystyrenes and Graft Polyisoprene/Polystyrene Copolymers with Double Branches (“Centipedes”). Quality of (1,3-Phenylene)bis(3-methyl-1-phenylpentylidene)dilithium Initiator in the Presence of Polar Additives , 1998 .

[146]  S. Armes,et al.  Synthesis and characterization of biocompatible thermo-responsive gelators based on ABA triblock copolymers. , 2005, Biomacromolecules.

[147]  J. Mays,et al.  2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization , 2017 .

[148]  D. Zhao,et al.  Thick wall mesoporous carbons with a large pore structure templated from a weakly hydrophobic PEO–PMMA diblock copolymer , 2008 .

[149]  Shiping Zhu,et al.  Polystyrene-block-poly(n-butyl acrylate)-block-polystyrene Triblock Copolymer Thermoplastic Elastomer Synthesized via RAFT Emulsion Polymerization , 2010 .

[150]  D. Zhao,et al.  Ultra-Large-Pore Mesoporous Carbons Templated from Poly(ethylene oxide)-b-Polystyrene Diblock Copolymer by Adding Polystyrene Homopolymer as a Pore Expander , 2008 .

[151]  R. Storey,et al.  Poly(styrene-b-isobutylene-b-styrene) block copolymers and ionomers therefrom: morphology as determined by small-angle X-ray scattering and transmission electron microscopy , 2000 .

[152]  Qiuyu Zhang,et al.  Synthesis and Characterization of Comb and Centipede Multigraft Copolymers PnBA-g-PS with High Molecular Weight Using Miniemulsion Polymerization , 2014 .

[153]  Christopher J. Ellison,et al.  Directed self-assembly of silicon-containing block copolymer thin films. , 2015, ACS applied materials & interfaces.

[154]  A. Hirao,et al.  Precise Synthesis of Block Polymers Composed of Three or More Blocks by Specially Designed Linking Methodologies in Conjunction with Living Anionic Polymerization System , 2013 .

[155]  U. Wiesner,et al.  Organically modified aluminosilicate mesostructures from block copolymer phases , 1997, Science.

[156]  A. Sokolov,et al.  Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids , 2016 .

[157]  Marcus Müller,et al.  Defects in the Self-Assembly of Block Copolymers and Their Relevance for Directed Self-Assembly. , 2015, Annual review of chemical and biomolecular engineering.

[158]  Simon Harrisson,et al.  The limits of precision monomer placement in chain growth polymerization , 2016, Nature Communications.

[159]  C. Hawker,et al.  Controlling Polymer-Surface Interactions with Random Copolymer Brushes , 1997, Science.

[160]  D. Hammer,et al.  Bioresorbable Vesicles Formed through Spontaneous Self-Assembly of Amphiphilic Poly(ethylene oxide)-block-polycaprolactone. , 2006, Macromolecules.

[161]  Adam Blanazs,et al.  Self-Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications. , 2009, Macromolecular rapid communications.

[162]  C. Liang,et al.  Mesoporous carbon materials: synthesis and modification. , 2008, Angewandte Chemie.

[163]  Bumjae Lee,et al.  Applications of 1,1-Diphenylethylene Chemistry in Anionic Synthesis of Polymers with Controlled Structures , 2000 .