Manning, and marcus weck macromolecules 2016 49 19, 71177128. Complementary quadruple hydrogen bonding in supramolecular. Due to the extraordinary range of properties accessible, polymers have come to play an essential and ubiquitous role in everyday life from plastics and elastomers on the one hand to. Mainchain supramolecular block copolymers chemical society.
Selfassembly of amphiphilic block copolymers in selective. This contribution introduces main chain supramolecular abc and abb. Supramolecular selfassembly of multiblock copolymers in aqueous solution michael d. Supramolecular helixhelix block copolymers anna croom, kylie b.
Supramolecular networks from block copolymers based on. This pioneering text provides not only a guideline for developing synthetic strategies for creating block copolymers with defined characteristics, but also a key to the relationship between the physical properties of block copolymers and the structure and dynamics of materials. Hacceptor copolymers p3 and p4 were complexed with different generations of dendritic hdonors g1coohg3cooh bearing 1,3,4oxadiazole oxd dendrons and terminal benzoic acids via hbonded selfassembly to form supramolecular side chain copolymers i. Booth c, yu ge, nace vm 2000 block copolymers of ethylene oxide and 1,2butylene oxide. Chain architecture can have a profound effect on the appearance of the. Molecularrecognitiondirected formation of supramolecular polymers.
Matrixfree polymer nanocomposite thermoplastic elastomers. Synthesis, thermal properties, and morphologies of. The strength of the forces responsible for spatial organization of the system range from weak intermolecular forces, electrostatic charge, or hydrogen bonding to strong covalent bonding, provided that the electronic coupling strength remains small relative to the energy. Supramolecular block copolymers for the synthesis of higher order nanostructured assemblies. Here we report the formation of supramolecular block copolymers by. Block copolymer bcp selfassembly is one of the most versatile concepts for the. Supramolecular micellization of diblock copolymer mixtures. Overview on an open zeroemission car nissan and a schematic view of a single h2fuel cell extracted from a stack.
Stress relaxation in supramolecular polymers also occurs by reptation, but additionally, supramolecular chains can release strain by breaking and then recombining with other, strain free chainends. The formation of a corona of hydrophilic segments surrounding the core of waterinsoluble segments is the reason for the prevention of progressive. In particular, metallosupramolecular block copolymerscopolymers in which the blocks are linked together by a metalligand complexhave seen important progresses, allowing better control over. Controlling the selfassembly structure of magnetic nanoparticles and amphiphilic blockcopolymers. This approach creates block copolymoc bcpmoc materials whose microscopic structures and mechanical properties are readily tunable by adjusting the size and geometry of the mocs and the composition of the bcps.
This first part covers newer developments in polymer synthesis, including living radical polymerization, catalytic chain transfer and free radical ringopening polymerization, along with strategies for the synthesis of conducting polymers, dendrimers, hyperbranched polymers and block copolymers. Supramolecular organization in block copolymers containing a conjugated segment. Supramolecular polymers, second edition details assembly processes and structurefunction correlation in natural and synthetic selfassembling materials, focusing on developments occurred over the past five years. Supramolecular organization in block copolymers containing a. The strength of the forces responsible for spatial organization of the system range from weak intermolecular forces, electrostatic charge, or hydrogen bonding to strong covalent bonding, provided that the electronic coupling strength remains small relative. The supramolecular polymerization of macromolecular repeating units affords a novel class of materials. Supramolecular chemistry from molecules to nanomaterials 2012 isbn. Mainchain supramolecular block copolymers chemical.
Polymers are huge macromolecules composed of repeating structural units. This is manifested in the area of block copolymer selfassembly where supramolecular and dynamic covalent polymers. Readers are advised to keep in mind that statements, data, illustrations. Oh end groups were converted to moieties able to form complementary hydrogen bonds including 2,6diaminopurine, dap, thymine, thy, and the socalled. Complementary quadruple hydrogen bonding in supramolecular copolymers. Mallapragada, department of chemical and biological engineering, iowa state university and ames laboratory. The ultimate tensile stress and elastic modulus increased with increasing ps chain length. One of the most intensively studied topics in the developing field of selfassembled block copolymers is the polymeric micelles formed in aqueous media from amphiphilic block copolymers. This book focuses on the area of metalcontaining polymers which, based on the. Block copolymocs by stepwise selfassembly journal of the. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials.
Supramolecular alternating block copolymers via metal. Supramolecular graft copolymers containing a quadruple hydrogen bond motif in the main chain have been prepared by acyclic diene metathesis admet polymerization of an. The next chapter defines block copolymers and compares them with other types of polymer hybrids, that is, polymer blends, random copolymers, and graft copolymers. Supramolecular assemblies of block copolymers in aqueous. The full text of this article hosted at is unavailable due to technical difficulties. Supramolecular selfassembly of multiblock copolymers in aqueous solution by michael duane determan. Many research groups have explored the properties and solution self. A block copolymers sustained by orthogonal metal coordination and hydrogen bonding between telechelic polymers that feature distinct secondary structure motifs. Supramolecular copolymers with stimuliresponsive sequence. The supporting information is available free of charge on the acs. Phase separation of supramolecular and dynamic block.
Due to their broad range of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Supramolecular multiblock copolymers featuring complex. Controlled polymerization techniques in combination with supramolecular assembly are used to engineer hetero. Kinetic studies on diblock copolymerization manifested a. The combination of controlled anionic polymerization and subsequent introduction of hydrogen bonding groups was established to form thermoreversible, supramolecular networks. Macro and microphase separation in block copolymer supramolecular assemblies induced by solvent annealing. Block copolymocs by stepwise selfassembly journal of. Supramolecular block copolymers under thermodynamic control article pdf available in journal of the american chemical society 14023 may 2018 with 88 reads how we measure reads. The optical properties are examined, whereby individual ppvs exhibit similar properties regardless of the nature of the end group. Selfassembly of block copolymers into internally ordered. This approach combines atomic force microscopy afm measurements on thin polymer deposits, which reveal the typical microscopic morphologies, and molecular.
Supramolecularhybridhydrogelsfromnoncovalentlyfunctionaliz. Controlling the morphology of side chain liquid crystalline block copolymer thin films through variations in liquid crystalline content. We report a stepwise assembly strategy for the integration of metalorganic cages mocs into block copolymers bcps. Rapid selfassembly of block copolymers to photonic. The book highlights developments in the synthesis of complex structures, chemical des. Gebel, blockionomer for fuel cell application in block copolymers in nanoscience lazzari, liu and lecommendoux ed. May 21, 2014 cocrystallization phase transformations in all. Chapter 2 block copolymers in this thesis, the lamellar orientation in thin lms of a symmetric diblock copolymer polystyrenepolymethylmethacylate psbmma under competing e ects of surface interactions and an electric eld applied perpendicular to the surfaces will be studied. Pdmabpnipam, we successfully prepared block copolymer grafted graphene sheets via inclusion complexation for the. Synthesis, thermal properties, and morphologies of amphiphilic brush block copolymers with tacticitycontrolled polyether main chain takuya isono, hoyeol lee, kana miyachi, yusuke satoh, toyoji kakuchi. There are two ways in which mainchain supramolecular polymers can. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as dna.
Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. Photoresponsive liquid crystalline block copolymers. The gelation behavior depended on the structure of the block copolymers. Nov 21, 2015 stimuliresponsive molecular materials, i.
Main chaintype block copolymers through atom transfer radical polymerization from doubledeckershaped polyhedral oligomeric silsesquioxane. Supramolecularhybridhydrogelsfromnoncovalentlyfunctionalized. Supramolecular conjugated block copolymers macromolecules. Block copolymers are key building blocks for a variety of applications ranging. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks re. Supramolecular polymers, second edition details assembly processes and structurefunction correlation in natural and synthetic selfassembling materials, focusing on developments occurred over the past five years the book highlights developments in the synthesis of complex structures, chemical design principles, and theoretical models of growth. Comprised of seven chapters, this book begins with an overview of what block copolymers are, how they are made, and what they can and cannot be expected to do.
The growing synergy between supramolecular chemistry and polymer synthesis is driven by the realization that the dynamic nature of noncovalent interactions may bring new properties and material performance to the field of polymer science. The solventfree microparticles contain an inner structure that corresponds to the bcp. Some of the possible copolymer architectures are shown in fig. Block copolymer micelles so far examined in aqueous media are composed of amphiphilic block copolymers, and the main driving force for the micellization in these cases is hydrophobic interaction. Massimo lazzari received his phd in macromolecular chemistry at the university of torino italy under the supervision of prof. Anionic polymerization techniques were employed for the synthesis of linear polystyrene ps and block copolymer of ps and polyisoprene pi psbpi bearing end hydroxyl groups. Onepot synthesis of brush copolymers bearing stereoregular.
Controlled polymerization techniques in combination with supramolecular assembly are used to engineer heterotelechelic. Hatada at the osaka university japan, where he learned the secrets of anionic polymerisation, in 1998 he became assistant professor at the university of torino, working on the. Study of supramolecular sidechain copolymers containing. Structure and composition revealed by theoretical modeling. The equilibrium morphology for a given block copoly.
Oh end groups were converted to moieties able to form complementary hydrogen bonds including 2,6diaminopurine, dap, thymine, thy. Part one formation of supramolecular polymers supramolecular polymer chemistry, first edition. Block copolymers, which are the main subject of this paper, could be incorporated into a large range. The solidstate supramolecular organization of block copolymers containing one pconjugated block and one nonconjugated block is elucidated with a joint experimental and theoretical approach. Lee yh1, chen wc, yang yl, chiang cj, yokozawa t, dai ca. A structure comprising a supramolecular assembly of a plurality of block copolymers. In supramolecular copolymers, this connection is replaced by a more labile, in some cases reversible, one hydrogen bonding, hostguest interaction, and metaltoligand complexation represent the most prominent and versatile examples in this respect. Supramolecular polymers 2nd edition alberto ciferri. Supramolecular organization in block copolymers containing. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers.
This is manifested in the area of block copolymer selfassembly where supramolecular systems have displayed remarkable morphologies and properties not attained in classic covalent systems. Hacceptor copolymers p3 and p4 were complexed with different generations of dendritic hdonors g1coohg3cooh bearing 1,3,4oxadiazole oxd dendrons and terminal benzoic acids via hbonded selfassembly to form supramolecular sidechain copolymers i. Supramolecular selfassembly of multiblock copolymers in. Pdf supramolecular block copolymers under thermodynamic. Alexandridis p, lindman b eds amphiphilic block copolymers. Supramolecular chemistry is the domain of chemistry concerning chemical systems composed of a discrete number of molecules. In classical block copolymers, the constituent blocks are linked via a covalent bond. Nanostructured supramolecular block copolymers based on polydimethylsiloxane and polylactide.
The dispersion of the silica nps and the microphase separation of the block copolymer in the matrix free polymer nanocomposite were investigated using smallangle xray scattering saxs, transmission electron microscopy tem, differential scanning. Hatada at the osaka university japan, where he learned the secrets of anionic polymerisation, in 1998 he became assistant professor at the university of torino, working on the characterisation and. These polymeric aggregates can exist in an equilibrium state between low and high molecular. The past few decades have seen a significant growth in the field of supramolecular polymerizations, in which reversible noncovalent interactions e. Polymers free fulltext main chaintype block copolymers. The selforganized supramolecular structure and chain behavior of a mixture of two diblock. Various kinds of amphiphilic blockcopolymers composed of a variety of hydrophilic and hydrophobic segments have so far been synthesized, and their selfassembly. Supramolecular polymers, where hydrogen bonds are the only force keeping the. Supramolecular selfassembly of multiblock copolymers. In particular, metallo supramolecular block copolymers copolymers in which the blocks are linked together by a metalligand complexhave seen important progresses, allowing better control over the. Copolymer sequence is another feature that can have an important impact on the macroscopic behavior of a polymer synthesized from more than a single monomer.
Abstracta series of azobased diblock copolymers dbcs with various compositions were successfully synthesized via reversible additionfragmentation chain transfer raft polymerization in anisole with pcaemacta macrocta, dopam new acrylamide monomer and aibn initiator. Fabrication of supramolecular semiconductor block copolymers. Thus we have developed a ph temperaturedependent, reversible hierarchically selfassembling block copolymer system with structures spanning nano to microscale dimensions. His main interest focuses on studying the mechanisms of supramolecular polymerizations, using chiral amplification as a tool for studying twocomponent systems. The resultant hybrid graphene inclusion complex hgic turned into supramolecular polymeric hydrogels upon heating.