Hyperbranched Organometallic Polyynes :Optical and Thermal Properties and Their Transformation into Soft Ferromagnetic Ceramics

1Introduction Organometallic polymers have emerged as a group of interesting materials due to their useful catalytic,optical, electrical, sensing, and magnetic properties inaccessible by their pure organic parents. It is therefore highly desirable to utilize this class of high performance macromolecules for the preparation of micro- and nanosized patterns by photolithographic techniques and as precursors for advanced ceramics[1].     

Synthesis and Properties of Photo-functional Hyperbranched Polymers

1 Results UV curing systems have been widely used in various industries such as coatings,printing inks,and photo-resists,because of their low volatile organic compound (VOC),excellent physical properties,and energy saving.Recently,these systems have also been applied to electronics and information technology fields such as display,CD,DVD,optical-fiber,and optical-device. In these curing systems,(meth)acrylate oligomers are mainly used due to their high photochemical reactivity. Recently,dendritic polymers have been of great interest in the field of polymer chemistry and chemical industry. Because these dendritic polymers have excellent characteristic properties such as low viscosity,good solubility and many functional groups,compared with corresponding linear polymers. Dendritic polymers were categorized two types such as dendrimers with the uniformed structures and hyperbranched polymers (HBP)s with randomly branched structure. The former polymers were synthesized by multi-step reactions with purification procedures,and the latter polymers were essentially synthesized by one-pot process. Therefore,HBPs have great possibility as high performance and new materials in UV technology fields. From this background,the author reports the synthesis and photochemical properties of novel hyperbranched polymers as follows.     

Hyperbranched Polysiloxysilanes

Hyperbranched polymers have been paid attention because of their unique structures. Especially, they have many terminals whose number is the same as that of repeating units as far as they are synthesized from AB2 type monomers. These characteristics of the hyperbranched polymers make them new functionalized polymers. Polysiloxanes have unique properties such as low Tg, high decomposition temperature, water repulsion, and good dielectric property. They are widely fabricated from liquid （oil） to solid （resin） by changing the extent of crosslinking. We have studied dendrimers and hyperbrached polymers possessing polysiloxane structure. These materials have the amphiphilic nature when they have amine functional group at the terminal position.     

Preparation and adsorption behaviors of Cu(II) ion-imprinted polymers

Imprinted polymers were prepared for selective removal of Cu(II) ions from metal solutions. Three ion-imprinted polymers were synthesized with methacrylic acid (MAA), acrylamide (AA) and N,N'-methylenebisacrylamide (MBAA) respectively as the functional monomers, ethleneglycoldimethacrylate (EGDMA) as the cross-linking agent, 2,2’-azobisisobutyronitrile (AIBN) as the initiator and Cu (II) ion as the imprint ion. The template Cu (II) ion was removed from the polymer by leaching with a liquid of a 1:1 volumetric ratio of HCl to ethylenediaminetetraacetic acid (EDTA). The capacity and selectivity of Cu(II) ion adsorption were investigated with the three imprinted polymers and their non-imprinted counterparts. The polymers have a maximum adsorption capacity at pH 7.0. The isotherm of their batch adsorption of Cu(II) ions shows a Langmuir adsorption pattern. Imprinted polymers all have a much higher capacity and higher selectivity of Cu(II) adsorption than non-imprinted ones. MAA polymer benefits the most from imprinting. Imprinted MAA polymer has the highest selectivity when used to rebind Cu (II) ion from an aqueous solution in the presence of other metal ions. Ion imprinting can be a promising technique of preparing selective adsorbents to separate and preconcentrate metal in a medium of multiple competitive metal ions through solid phase extraction (SPE).     

The Mechanism of Cumene Peroxidation Catalyzed by Cobalt(Ⅱ)-Chelated Copolymer

1Introduction The functionalised polymers, especially for chelating polymer, have been employed to considerable effects in organic synthesis for several decades. The use of polymer groups as ligands permits the ligand surroundings to be varied and regulation of the catalytic properties of the complexes because of the flexibility of the polymer chains, their ability to adopt various conformations, and the possibility of creating various spatial distributions of metal centers immobilized on the polymer chains[1,2]. In our recently studies[3-5], the chelating copolymer with imino-diacetic acid chelating group in the polymer side chain was manufactured, and which can increase effectively amount of the chelating group within the polymer. Meanwhile, the high catalysis performance in organic synthesis had also been proved via benzaldehyde and cumene peroxidation. For cumene peroxidation,it is hardly to find such a simple catalyst with high conversion and selectivity due to hydroperoxide decomposition by a radical mechanism. The cumene peroxidation by catalyst system and its reaction mechanism as well as the kinetic study are popularly investigated object for many researchers[6-9]. However, the reaction mechanism still does not clear owing to the by-products will be produced following the different catalysts used.     

Design of Smart Polymer-Protein Conjugates and Smart Magnetic Nanoparticles for Use in Microfluidic Diagnostic Assays

1 Results In this talk,I will describe the design,synthesis and application of smart polymers for use in microfluidic diagnostic devices.We are synthesizing a variety of temperature- and pH-responsive polymers using RAFT living free radical polymerization techniques.This allows us to control molecular weight and to achieve a narrow MW distribution of the polymers. Furthermore,RAFT polymers have reactive end groups that are used to conjugate the polymers to proteins.We are also using those groups to bind and coat the smart polymers onto the surfaces of polymeric or magnetic nanoparticles.We have applied UV graft co-polymerization techniques to coat the channel surfaces in the microfluidic devices with the smart polymers.The smart polymers we work with include temperature-responsive polymers such as poly(N-isopropyl acrylamide) or PNIPAAm and pH-responsive polymers such as poly(propylacrylic acid) or PPAA.We are synthesizing random,block and graft copolymers of these compositions as well.     

Self-Assembled Conjugated Polymer Nanometer Scale Devices

1 Introduction Nanometer scale devices, as the next generation devices of electronics, have got a worldwide attention and rapid development recently. Simultaneously, conjugated polymers have been applied in organic electronics successfully because of their outstanding electronic-photonic properties. However, as far as we know few reports have dealt with the fabrication of nanometer scale devices by using conjugated polymers, although the combination of nanometer scale devices and polymers will…     

Supramolecular Organization of Porphyrin and Phthalocyanine by Complementary Coordination

1 Results We have already established a methodology of supramolecular organization of porphyrin and phthalocyanine by complementary coordination of the imidazolyl substituent to their metal centers.Since the stability constants reached a range of 1011 to 1012 M-1 in nonpolar solvents,it allowed construction of stable structures such as special pair of photosynthetic reaction center and light-harvesting antenna complex of photosynthetic bacteria.Here,we report one-dimensional array of porphyrin for the development of molecular wire and porphyrin-phthalocyanine conjugate as a molecular memory.     

A New Route to Hyperbranched Macromolecules :Syntheses of Photosensitive Poly(aroylarylene)s via Regioselective Polycyclotrimerization of Bis(aroylacetylene)s

1Introduction Because of their unique molecular architecture, hyperbranched polymers (hb-Ps) are envisioned to exhibit novel properties, unachievable by their linear congeners, and to serve as advanced functional materials. Realization of the full potential of hb-Ps calls for the exploration of new, versatile methods for their syntheses.     

Progress in the Supramolecular Architecture-directed Synthesis of Perfect Ladder Polysiloxanes

1 Introduction Ladder polysiloxanes (LPSs) including organo-bridged ladder polyorganosiloxanes (R-OLPSs, R is side group) and ladder polyorganosilsesquioxanes (R-LPSQs) have intrigued polymer chemists for about 50 years due to their excellent resistance to all kinds of degradations. However, their synthesis has been a great challenge to polymer chemists. Here, we describe a new approach based on supramolecular concerted interactions as follows.2 Results2.1 Synthesis of Perfect R-OLPSsA series of real OLPSs have been successfully prepared by different kinds of concerted effects of H-bonding, aromatic π-π stacking and/or donor-acceptor interactions, respectively[1-4].     

New Approach to the Synthesis of C-Glycosides

C-glycosides are important carbohydrate mimetics and have gained considerable attention because ot their attractive biological activities as pharmaceutical targets and their resistance to enzymatic degradation in vivo. Consequently, a large number of C-glycosides have been synthesized for their bioactivity investigation, and various synthetic methodologies have been developed. As a continuation of the synthesis of novel C-glycoside derivatives using exo-glycals as the precursor, we wish to present herein new approaches to the synthesis of C-aryl aminoglycoside via the 1,3-dipolar cycloaddition （Scheme 1 ） and C-disaccharides by Suzuki cross-coupling reaction （Scheme 2）, and the synthesis of dihydropyrimidinonyl （DHPM） glycoside by the three component Biginelli reaction （Scheme 3）.     

Characteristics and mechanism of abrasive wear for thermoplastic polymers

Abrasive wear characteristics of polyethylene, polystyrene, polymethylmethacrylate, nylon 1010 and polyvinyl chloride were investigated. The volume relative wear resistance coefficients of these thermoplastic polymers are 18%-35% (hardened and low temperature tempered steel 45 was used as a comparing material), and have a linear correlation with square roots of their cohesive energy densities. The coefficients of linear correlation is 0.949. Wear morphologies were observed by scanning electron microscope (SEM). Main wear mechanism of the thermoplastic polymers includes brittle breaking for the hard and brittle polymers & plowing and fatiguing for the soft and tough ones.     

Effect of Coordinate Bond in Molecular Recognition of Enrofloxacin with Imprinted Polymers

1 Results Molecular imprinting is a technique for the preparation of functional materials with molecular recognition properties.Molecular imprinted polymers (MIPs) have become an increasingly active field of study for the construction of new material capable of molecular recognition.In general,MIPs are synthesized by polymerization of cross-linking complexes of template molecules and functional monomers.After removing the template molecules from de polymers,binding sites are formed by functional monomer derived residues complementary for the template molecules[1]. According to the principle,the stability of monomer-template complexes present in the solution prior to polymerization as well as the polymerization reaction itself undoubtedly play a dominant role in determining the recognition performance of the polymer.     

A New Route to Hyperbranched Macromolecules ：Syntheses of Photosensitive Poly（aroylarylene）s via Regioselective Polycyclotrimerization of Bis（aroylacetylene）s

Because of their unique molecular architecture, hyperbranched polymers （hb-Ps） are envisioned to exhibit novel properties, unachievable by their linear congeners, and to serve as advanced functional materials. Realization of the full potential of hb-Ps calls for the exploration of new, versatile methods for their syntheses.     

Synthesis of Telechelic Polyisobutylenes and Polyethers and Their Characterization

Telechelic polymers have attained great consideration as building blocks in the synthesis of block copolymers and networks. Telechelic polymers with various endgroups are also widely used materials for the preparation of polymeric prodrugs. Several methods have been reported to obtain functionalized polymers from the corresponding polyisobutylene （PIB） and polyether derivatives. In this presentation, we will demonstrate very versatile and powerful synthetic methods to obtain telechelic polymers.     

Development of Polymer Electrolyte Membranes for High Temperature PEFCs

1 Introduction During the last decades the research has been devoted to the development of non-perfluorinated polymers[1,2], as an alternative to commercial perfluorosulphonic membranes. There are several non-perfluorinated materials suitable for these systems that should have as a fundamental requirement a good thermal stability of the original polymer. The studied polymers consist of polyaromatic or polyetherocyclic repeat units like polyetheretherketone (PEEK). Many papers have been published about the properties of this class of polymers, especially for PEEK functionalisation by the insertion of sulphonic groups[3] and for the preparation of composite membranes[4], even if they generally show lower proton conductivity than Nafion at the requested operative temperatures.Polymer inorganic composite membranes are interesting because many of the inorganicadditives used are able to operate at much higher temperatures than pure polymers. Some of the possible advantages of incorporating inorganic compounds into composite membranes include, enhanced proton conductivity, water retention at hightemperatures, and mechanical resistance.     

Water-free Alkaline Polymer-inorganic Acid Complexes with High Conductivity at Ambient Temperature

1 Results Recently increased interest is shown to proton conducting materials based on the alkaline polymer-inorganic acid complexes that is caused by a possibility of their application as the high-temperature electrolyte systems for various electrochemical devices (fuel cells,sensors,lithium power sources etc.).Complexes of inorganic acids with the alkaline polymers (polybenzimidazoles[1],polyvinylpyridines[2]) are characterized by high ionic conductivity at ambient temperatures (up to 10-2 Ω-1·cm-1) and thermal stability up to 200 ℃.However during the work of a fuel cell there is a problem of an opportunity of an acid washing away from a membrane,and,as a consequence,decreasing of the performance characteristics of the electrochemical device.     

Virtual Reality As a New Tool in the City Planning Process

The introduction of virtual reality (VR)-models in the city planning process will cause changes in the traditional roles of the involved parties. In order to better understand some of these changes, the events involving the use of VR-models in an architectural competition concerning rebuilding-proposals for the city library in a Swedish city were analyzed. The study shows that VR was introduced into the competition as an extra add-on and that the VR-presentation was experienced as useful by the jury. The transformation of the architects’ contributions into VR was experienced as problematic by the architects, partly because they lost full control over the presentation. In the future architects are likely to have to produce the VR-models for their proposals themselves. This may make it more difficult for smaller architectural firms to enter the market but their proposals will be more accessible to a wider group of stakeholders.     

The Mechanism of Cumene Peroxidation Catalyzed by Cobalt（ Ⅱ ）-Chelated Copolymer

1 Introduction The functionalised polymers, especially for chelating polymer, have been employed to considerable effects in organic synthesis for several decades. The use of polymer groups as ligands permits the ligand surroundings to be varied and regulation of the catalytic properties of the complexes because of the flexibility of the polymer chains, their ability to adopt various conformations, and the possibility of creating various spatial distributions of metal centers immobilized on the…     

Synthesis and Thermal Property of the Poly（silpheny-lenesiloxane）s with Functional Groups

1 Introduction Silicon-containing polymers have been intensively studied in the past half-century, and a great number of papers, patents and books have been published on the synthesis, properties and applications. Silicon-containing polymers, especially polymers containing silicon atoms in the backbone, including some major species as polysiloxane, polysilane, polysilazane, etc. have chains constructed of alternately arranged silicon and oxygen atoms with organic groups attached to the silicon…