• Title/Summary/Keyword: Block copolymers

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Preparation of Copolymers by Controlled Radical Polymerization and their Applications

  • Choi, Kil-Yeong;Kim, Yong-Seok;Han, Seung-San;Lee, Jae-Heung
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.95-96
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    • 2006
  • Surface modification of clay minerals has become increasingly important for improving the practical applications of clays such as polymeric nanocomposites. We used the copolymer as modifiers having phenyl components, and successfully developed a route for the preparation of amine functionalized polymer based on oligostyrene and its block copolymers. The oligo(St-co-VBC)s with controlled molecular weight were synthesized via nitroxide mediated polymerization method. We also successfully prepared organophilic layered silicates whose surface is covered with styrenic copolymers. Through the analysis of chemical structure and morphology, we concluded that copolymers were very effective organic modifiers to change the surface characteristics of layered silicates.

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Synthesis of Star like Random Copolymers from Resorcinarene-based Alkoxyamine Initiator via Nitroxide Mediated Free Radical Polymerization

  • Abraham, Sinoj;Choi, Jae-Ho;Ha, Chang-Sik;Kim, Il
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.337-337
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    • 2006
  • The synthesis of an octafunctional resorcinarene based initiator for nitroxide mediated polymerization and its ability to yield random star copolymers of styrene and methyl methacrylate is studied. The effect of the initiator conformations towards its activity and the conditions that permit the formation of well-defined star block copolymers is also investigated in detail. The characterization of the initiator and the polymers were carried out by various spectro-analytical techniques. Well-defined random copolymers were obtained with controlled molecular weight and low PDI depending on the monomer feed.

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Synthesis and Design of Electroactive Polymers for Improving Efficiency and Thermal Stability in Organic Photovoltaics

  • Kim, Beom-Jun
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2011.05a
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    • pp.11.2-11.2
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    • 2011
  • Polymer based organic photovoltaics have attracted a great deal of attention due to the potential cost-effectiveness of light-weight and flexible solar cells. However, most BHJ polymer solar cells are not thermally stable as subsequent exposure to heat drives further development of the morphology towards a state of macrophase separation in the micrometer scale. Here we would like to show three different approaches for developing new electroactive polymers to improve the thermal stability of the BHJ solar cells, which is a critical problem for the commercialization of these solar cells. For one of the examples, we report a new series of functionalized polythiophene (PT-x) copolymers for use in solution processed organic photovoltaics (OPVs). PT-x copolymers were synthesized from two different monomers, where the ratio of the monomers was carefully controlled to achieve a UV photo-crosslinkable layer while leaving the ${\pi}-{\pi}$ stacking feature of conjugated polymers unchanged. The crosslinking stabilizes PT-x/PCBM blend morphology preventing the macro phase separation between two components, which lead to OPVs with remarkably enhanced thermal stability. The drastic improvement in thermal stabilities is further characterized by microscopy as well as grazing incidence X-ray scattering (GIXS). In the second part of talk, we will discuss the use of block copolymers as active materials for WOLEDs in which phosphorescent emitter isolation can be achieved. We have exploited the use of triarylamine (TPA) oxadiazole (OXA) diblock copolymers (TPA-b-OXA), which have been used as host materials due to their high triplet energy and charge-transport properties enabling a balance of holes and electrons. Organization of phosphorescent domains in TPA-b-OXA block copolymers is demonstrated to yield dual emission for white electroluminescence. Our approach minimizes energy transfer between two colored species by site isolation through morphology control, allowing higher loading concentration of red emitters with improved device performance. Furthermore, by varying the molecular weight of TPA-b-OXA and the ratio of blue to red emitters, we have investigated the effect of domain spacing on the electroluminescence spectrum and device performance.

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Polystyrene-b-poly(oligo(ethylene oxide) Monomethyl Ether Methacrylate)-b-polystyrene Triblock Copolymers as Potential Carriers for Hydrophobic Drugs

  • You, Qianqian;Chang, Haibo;Guo, Qipeng;Zhang, Yudong;Zhang, Puyu
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.558-564
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    • 2013
  • A simple and effective method is introduced to synthesize a series of polystyrene-b-poly(oligo(ethylene oxide) monomethyl ether methacrylate)-b-polystyrene (PSt-b-POEOMA-b-PSt) triblock copolymers. The structures of PSt-b-POEOMA-b-PSt copolymers were characterized by Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance ($^1H$ NMR) spectroscopy. The molecular weight and molecular weight distribution of the copolymer were measured by gel permeation chromatography (GPC). Furthermore, the self-assembling and drug-loaded behaviours of three different ratios of PSt-b-POEOMA-b-PSt were studied. These copolymers could readily self-assemble into micelles in aqueous solution. The vitamin E-loaded copolymer micelles were produced by the dialysis method. The micelle size and core-shell structure of the block copolymer micelles and the drug-loaded micelles were confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The thermal properties of the copolymer micelles before and after drug-loaded were investigated by different scanning calorimetry (DSC). The results show that the micelle size is slightly increased with increasing the content of hydrophobic segments and the micelles are still core-shell spherical structures after drug-loaded. Moreover, the glass transition temperature (Tg) of polystyrene is reduced after the drug loaded. The drug loading content (DLC) of the copolymer micelles is 70%-80% by ultraviolet (UV) photolithography analysis. These properties indicate the micelles self-assembled from PSt-b-POEOMA-b-PSt copolymers would have potential as carriers for the encapsulation of hydrophobic drugs.

Si-Containing Nanostructures for Energy-Storage, Sub-10 nm Lithography, and Nonvolatile Memory Applications

  • Jeong, Yeon-Sik
    • Proceedings of the Korean Vacuum Society Conference
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    • 2012.08a
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    • pp.108-109
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    • 2012
  • This talk will begin with the demonstration of facile synthesis of silicon nanostructures using the magnesiothermic reduction on silica nanostructures prepared via self-assembly, which will be followed by the characterization results of their performance for energy storage. This talk will also report the fabrication and characterization of highly porous, stretchable, and conductive polymer nanocomposites embedded with carbon nanotubes (CNTs) for application in flexible lithium-ion batteries. It will be presented that the porous CNT-embedded PDMS nanocomposites are capable of good electrochemical performance with mechanical flexibility, suggesting these nanocomposites could be outstanding anode candidates for use in flexible lithium-ion batteries. Directed self-assembly (DSA) of block copolymers (BCPs) can generate uniform and periodic patterns within guiding templates, and has been one of the promising nanofabrication methodologies for resolving the resolution limit of optical lithography. BCP self-assembly processing is scalable and of low cost, and is well-suited for integration with existing semiconductor manufacturing techniques. This talk will introduce recent research results (of my research group) on the self-assembly of Si-containing block copolymers for the achievement of sub-10 nm resolution, fast pattern generation, transfer-printing capability onto nonplanar substrates, and device applications for nonvolatile memories. An extraordinarily facile nanofabrication approach that enables sub-10 nm resolutions through the synergic combination of nanotransfer printing (nTP) and DSA of block copolymers is also introduced. This simple printing method can be applied on oxides, metals, polymers, and non-planar substrates without pretreatments. This talk will also report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by the self-assembly of Si-containing BCPs. This approach offers a practical pathway to fabricate high-density resistive memory devices without using high-cost lithography and pattern-transfer processes. Finally, this talk will present a novel approach that can relieve the power consumption issue of phase-change memories by incorporating a thin $SiO_x$ layer formed by BCP self-assembly, which locally blocks the contact between a heater electrode and a phase-change material and reduces the phase-change volume. The writing current decreases by 5 times (corresponding to a power reduction of 1/20) as the occupying area fraction of $SiO_x$ nanostructures varies.

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Synthesis of Low Molecular-weight Poly (Propylene Carbonate)-Poly (Ethylene Glycol) Block Copolymers through $CO_2$/Propylene Oxide Copolymerization (이산화탄소/프로필렌 옥사이드 공중합을 통한 저분자량 폴리(프로필렌 카보네이트)-폴리(에틸렌 글리콜) 블록 공중합체의 합성)

  • Lee, Sang-Hwan;Cyriac, Anish;Jeon, Jong-Yeob;Lee, Bun-Yeoul
    • Clean Technology
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    • v.17 no.3
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    • pp.244-249
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    • 2011
  • We synthesized low molecular-weight polymers bearing hydrophobic and hydrophilic parts in a chain through $CO_2$/propylene oxide copolymerization. When hydrophilic poly (ethylene glycol) bearing -OH group (s) at the end group (s) was added as a chain transfer agent in the $CO_2$/propylene oxide copolymerization catalyzed by a highly active catalyst, block polymers were formed. If poly (ethylene glycol) (PEG) bearing -OH group only at an end was fed, PEG-block-PPC diblock copolymer was obtained. When PEG bearing -OH group at both ends was fed, PPC-block-PEG-block-PPC triblock copolymer was obtained. We confirmed formation of block copolymers by $^1H$-NMR spectroscopy and GPC studies.

Low Cost, Large Area Nanopatterning via Directed Self-Assembly

  • Kim, Sang-Uk
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.02a
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    • pp.24-25
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    • 2011
  • Molecular self-assembly has several advantages over other nanofabrication methods. Molecular building blocks ensure ultrafine pattern precision, parallel structure formation allows for mass production and a variety of three-dimensional structures are available for fabricating complex structures. Nevertheless, the molecular interaction for self-assembly generally relies on weak forces such as van der Waals force, hydrogen bonding, or hydrophobic interaction. Due to the weak interaction, the structure formation is usually slow and the degree of ordering is low in a self-assembled structure. To promote self-assembly, directed assembly methods employing prepatterned substrates or external fields have been developed and gathered a great deal of technological attention as a next generation nanofabrication process. In this presentation a variety of directed assembly methods for soft nanomaterials including block copolymers, peptides and carbon nanomaterials will be introduced. Block copolymers are representative self-assembling materials extensively utilized in nanofabrication. In contrast to colloid assembly or anodized metal oxides, various shapes of nanostructures, including lines or interconnected networks, can be generated with a precise tunability over their shape and size. Applying prepatterned substrates$^{1,2}$ or introducing thickness modulation$^3$ to block copolymer thin films allowed for the control over the orientational and positional orderings of self-assembled structures. The nanofabrication processes for metals, semiconductors$^4$, carbon nanotubes$^{5,6}$, and graphene$^{6,7}$ templating block copolymer self-assembly will be presented.

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Conformational Transition of Poly(γ-benzyl-L-glutamate)-Poly(ethylene glycol) Block Copolymers in Bulk

  • Choi, Young-Wook;Park, Young-Mi;Choo, Jae-Bum;Cho, Chong-Su;Sohn, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.28 no.5
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    • pp.795-799
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    • 2007
  • The bulk properties of poly(γ-benzyl-L-glutamate)-poly(ethylene glycol), PBLG-PEO, diblock copolymer were investigated. The helical transition from 7/2 to 13/5 for pure PBLG was at 120 oC while those of GE-1 and GE-2, which contain flexible PEO block 40 wt% and 60 wt% respectively, were shown at 135℃ on DSC experiments. FT-IR and XRD experiments were shown that the diblock copolymers maintained their α-helical structure in the temperature range between 25℃ and 175℃. Increasing relative size of coil part resulted in the increase of intermolecular packing distances. Due to well-maintained helical structure, lyotropic LC phases were observed for the PBLG-PEO block copolymer by the polarized optical microscope (POM). Especially, GE-3 copolymer, which has 12.5 wt% PEO contents, showed the smectic C phase. The competition of favorable aggregation energy between rod-rod and coil-coil, and unfavorable aggregation energy of rod-coil give rise to change the supramolecular structure in mixed solvent.

Synthesis and Characterization of Polyurethanes Based on Macromers (Macromer를 기초로 한 폴리우레탄의 합성 및 특성)

  • Chun, Y.C.;Kim, K.S.;Shin, J.S.;Kang, S.H.
    • Elastomers and Composites
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    • v.27 no.3
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    • pp.161-173
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    • 1992
  • A series of polyurethane block copolymers based on hydroxyterminated poly(dimethyl siloxane), poly(propylene glycol) and poly(tetramethylene glycol) soft segments of molecular weights 1,809, 2,000 and 2,000, respectively, were synthesized. The hard segments consisted of 4,4'-diphenylmethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize poly(dimethyl siloxane)-based polyurethane(PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure PDMS-PU, poly(propylene glycol)-based polyurethane(PPG-PU) and poly(tetramethylene glycol)-based polyurethane(PTMG-PU), (mixed polyol)-based block copolymers and blends between PDMS-PU, PPG-PU and PTMG-PU were prepared, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based PU and in lower hard segment content blends, macro-phase separation was shown, but blends with higher hard segment contents showed significant reduction in amounts of phase separation.

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