• Title/Summary/Keyword: microphase separation.

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Phase Behavior of Reversibly Associating Star Copolymer-like Polymer Blends

  • June Huh;Kim, Seung-Hyun;Jo, Won-Ho
    • Macromolecular Research
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    • v.10 no.1
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    • pp.18-23
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    • 2002
  • We theoretically consider blends of two monodisperse one-end-functionalized homopolymers (denoted by A and B) capable of forming clusters between functional groups (stickers) using weak segregation theory. In this model system resulting molecular architectures via clustering resemble star copolymers having many A- and B-arms. Minimizing the total free energy with respect the cluster distribution, the equilibrium distribution of clusters is obtained and used for RPA (Random Phase Approximation) equations as input. For the case that polymers are functionalized by only one kind of sticker, the phase diagrams show that the associations promote the macrophase separation. When there is strong affinity between stickers belonging to the different polymer species, on the other hand, the phase diagram show a suppression of the macrophase separation at the range of high temperature regime, as well as the phase coexistence between a disordered and a mesoscopic phase at the relatively lower temperatures.

Supramolecular Assembly toward Organic Nanostructures

  • Lee, Myong-Soo
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.173-173
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    • 2006
  • We have explored a strategy to control the supramolecular nano-structures self-assembled from rigid segments through attachment of flexible chains through microphase separation and anisotropic arrangement. Supramolecular structures formed by self-assembly of rigid building blocks can be precisely controlled from 1-D layered, 3-D bicontinuous cubic to 2-D cylindrical structures by systematic variation of the type and relative length of the respective blocks. Furthermore, depending on the individual molecular architectures, rigid building blocks self-assemble into a wide range of supramolecular structures such as honeycomb, disk, cylinder, helix, tube, barrel stave, and nano-cage.

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Sythesis and Properties of Liquid Crystalline Polyurethane Elastomers

  • Lee, Tae-Jung;Lee, Dong-Jin;Kim, Han-Do
    • Proceedings of the Korean Fiber Society Conference
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    • 1998.10a
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    • pp.98-101
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    • 1998
  • Segmented polyurethane elastomers are an important class of polymeric materials consisting of thermodynamically incompatible hard and soft segments. Due to the chemical structural difference between the hard and soft segments, a microphase separation occurs, consisting of crystalline hard domains and amorphous soft domains. (omitted)

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Preparation of Polysiloxane Composite Films with Microphase-Separated Silicone Oiol by Photocrosslinking (광가교 반응에 의한 미세 상 분리된 실리콘 오일을 함유하는 폴리실록산 복합체 필름의 제조)

  • 이정분;김정수;강영구;김동욱;이창진
    • Polymer(Korea)
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    • v.27 no.1
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    • pp.3-8
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    • 2003
  • Polysiloxanes with methacrylate groups at both terminals were synthesized by a hydrosilylation reaction between allyl methacrylate and hydride-terminated polysiloxanes. The polysiloxane methacrylates with high molecular weights could be prepared through the reaction of polysiloxane methacrylates and octamethylcyclotetrasiloxane with an acid catalyst. The structures of the prepared polysiloxane methacrylates were verified by $^1$H- and $^{29}Si-NMR.$ The polysiloxane methacrylates were freely miscible with silicone oils. Polysiloxane films with microphase-separated liquid silicone oil were prepared by photo-crosslinking the mixture of polysiloxane methacrylates and silicone oil. Scanning electron microscopy (SEM) of the films showed that the size of silicone oil droplets became smaller with a lower loading of silicone oil, lower molecular weight of polysiloxane methacrylate, and lower molecular weight of silicone oil.

Synchrotron SAXS Study on the Micro-Phase Separation Kinetics of Segmented Block Copolymer

  • Lee, Han-Sup;Yoo, So-Ra;Seo, Seung-Won
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.98-107
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    • 2001
  • The phase transition behavior isothermal micro-phase separation kinetics of polyester-based thermoplastic elastomer were studied using the synchrotron X-ray scattering(SAXS) method. The structural changes occurring during heating period were investigated by determining the changes of the one-dimensional correlation function, interfacial thickness and Porod constant. Based on the abrupt increases of the domain spacing and interfacial thickness, a major structural change occurring well below the melting transition temperature is suggested. Those changes are explained in terms of melting of the thermodynamically unstable hard domains or/and the interdiffusion of the hard and soft segments in the interfacial regions. SAXS profile changes during the micro-phase separation process were also clearly observed at various temperatures and the separation rate was found to be sensitively affected by the temperature. The peak position of maximum scattering intensity stayed constant during the entire course of the phase separation process. The scattering data during the isothermal phase separation process was interpreted with the Cahn-Hilliard diffusion equation. The experimental data obtained during the early stage of the phase separation seems to satisfy the Cahn-Hilliard spinodal mechanism. The transition temperature obtained from the extrapolation of the diffusion coefficient to zero value turned out to be about 147$\pm$$2^{\circ}$, which is close to the order-disorder transition temperature obtained from the Porod analysis. The transition temperature was also estimated from the inveriant growth rate. By extrapolating the inveriant growth rate to zero, a transition temperature of about 145$\pm$$\pm$$2^{\circ}$ was obtained.

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Thermally Stable Antireflective Coatings based on Nanoporous Organosilicate

  • Kim, Su-Han;Cho, Jin-Han;Char, Kook-Heon
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.282-282
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    • 2006
  • Nanoporous organosilicate thin films were realized by the microphase separation of pore generating components mixed with an organosilicate matrix. The refractive index of such nanoporous organosilicate films can be tuned in the range of $1.40{\sim}1.22$. With a nanoporous single layer with n ${\sim}1.225,\;99.85\;%$ transmittance in the visible range was achieved. In order to overcome the limitation on the narrow wavelength for high transmittance imposed by single nanoporous thin films, bilayer thin films with different reflectance for each layer were prepared by inserting high refractive index layer with a refractive index of 1.447. It is demonstrated that the novel broadband antireflection coating with improved transmittance can be easily achieved by the nanoporous bilayer thin films described in present study.

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Thermoplastic Polyurethane (TPU)/Ethylene-Propylene-Diene Monomer Rubber (EPDM) and TPU/Polybutadiene Rubber (BR) Blends for the Application of Footwear Outsole Materials (신발겉창 재료용 열가소성 폴리우레탄 (TPU)/에틸렌-프로필렌-디엔 고무와 TPU/부타디엔 고무 블렌드)

  • Kim, Ji-Hoo;Kim, Gue-Hyun
    • Elastomers and Composites
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    • v.48 no.3
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    • pp.195-200
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    • 2013
  • The main objective of this study is to improve abrasion resistance and wet slip resistance of thermoplastic polyurethane (TPU) by blending with ethylene-propylene-diene monomer rubber (EPDM) or polybutadiene rubber (BR) for the application of the footwear outsole materials. With addition of 10 wt% of EPDM or BR, TPU/EPDM and TPU/BR blends exhibited higher NBS abrasion resistance, tensile properties and wet slip resistance than TPU. However, with further increasing content of EPDM and BR, abrasion resistance and tensile properties of the blends decreased. Improvement in abrasion resistance and tensile properties with 10 wt% of addition of EPDM or BR may be due to better microphase separation of TPU.

Control of Mechanical Properties of Polyurethane Elastomers Synthesized with Aliphatic Diisocyanate Bearing a Symmetric Structure

  • Kojio, Ken;Nozaki, Shuhei;Takahara, Atsushi;Yamasaki, Satoshi
    • Elastomers and Composites
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    • v.54 no.4
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    • pp.271-278
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    • 2019
  • Polyurethane elastomers (PUEs) were synthesized using trans-1,4-bis(isocyanatomethyl) cyclohexane (1,4-H6XDI), poly(oxytetramethylene) glycol, 1,4-butanediol (BD), and 1,1,1-trimethylol propane (TMP). To control the molecular aggregation state and mechanical properties of these PUEs, hard segment contents of 20 and 30 wt% and BD/TMP ratios of 10/0 and 8/2 were chosen. Differential scanning calorimetry and small-angle X-ray scattering measurements revealed that the degree of microphase separation increased with an increase in both hard segment content and BD ratio. The Young's modulus and strain at break of the 1,4-H6XDI-based PUE were 6-20 MPa and 5-15, respectively. Incorporation of 20% TMP as a cross-linking agent into BD increased the melting temperature of the hard segment chains, that is, heat resistance, and decreased the Young's modulus. This could be due to the low density of the physical cross-linking network and the dispersion of hard segment chains in the soft segment matrix in the PUE in the presence of 20% TMP.

Kinetic Studies on Homopolymerization of $\alpha$-Methylstyrene and Sequential Block Copolymerization of Isobutylene with $\alpha$-Methylstyrene by Living/Controlled Cationic Polymerization (리빙/조절 양이온중합에 의한 알파메틸스티렌 호모중합 및 이소부틸렌과의 블록공중합에 대한 반응속도론 연구)

  • Wu, Yibo;Guo, Wenli;Li, Shuxin;Gong, Huiqing
    • Polymer(Korea)
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    • v.32 no.4
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    • pp.366-371
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    • 2008
  • The controlled/living cationic polymerization of $\alpha$-methylstyrene (${\alpha}MeSt$) and sequential block copolymerization of isobutylene (IB) with ${\alpha}MeSt$ were achieved using 2-chloro-2,4,4-trimethylpentane (TMPCl)/titanium tetrachloride ($TiCl_4$)/titanium isopropoxide ($Ti(OiPr)_4$)/2,6-ditert-butylpyridine (DtBP) initiating system in $CH_3Cl$/hexane(50/50 v/v) solvent mixture at $-80^{\circ}C$. The polymerization rate decreased with increasing $[Ti(OiPr)_4]/[TiCl_4]$ ratio in the homopolymerization of ${\alpha}MeSt$. The effects of $[Ti(OiPr)_4]/[TiCl_4]$ ratios and $PIB^+$ molecular weight on the polymerization rate and blocking efficiency were also investigated. Well-defined poly(isobutylene-b-$\alpha$-methylstyrene)s were demonstrated by $^1H$-NMR and triple detection SEC; refractive index (RI), multiangle laser light scattering (MALLS) and ultraviolet (UV) detectors. Blocking efficiencies for the poly(isobutylene-b-$\alpha$-methylstyrene)s of almost 100% were obtained when ${\alpha}MeSt$ was induced by PIB's of $M_n\;{\geq}\;41000$ at $[Ti(OiPr)_4]/[TiCl_4]=1$. Differential scanning calorimetry (DSC) of the block copolymers showed two glass transition temperatures, thereby demonstrating microphase separation.