• Macromolecular Research
• /
• v.15 no.6
• /
• pp.553-559
• /
• 2007

Nanocomposite films were prepared by sol-gel synthesis from vanadium triisopropoxide with $poly((oxyethylene)_9$ methacrylate)-graft-poly(dimethyl siloxane), POEM-g-PDMS, producing in situ growth of vanadium oxide within the continuous ion-conducting POEM domains of micro phase-separated graft copolymer. The formation of vanadium oxide was confirmed by wide angle x-ray scattering (WAXS) and Fourier transform infrared (FT-IR) spectroscopy. Small angle x-ray scattering (SAXS) revealed the spatially-selective incorporation of vanadium oxide in the POEM domains. Upon the incorporation of vanadium oxide, the domain periodicity of the graft copolymer monotonously increased from 17.2 to 21.0 nm at a vanadium content 14 v%, above which it remained almost invariant. The selective interaction of vanadium oxide with POEM was further verified by differential scanning calorimetry (DSC) and FT-IR spectroscopy. The nanocomposite films exhibited excellent mechanical properties $(l0^{-5}-10^{-7}dyne/cm^2)$, mostly due to the confinement of vanadium oxide in the POEM chains as well as the interfaces created by the microphase separation of the graft copolymer.

• Macromolecular Research
• /
• v.16 no.7
• /
• pp.609-613
• /
• 2008

Poly($\varepsilon$-caprolactone)-poly(ethylene glycol)-poly($\varepsilon$-caprolactone) (PCL-PEG-PCL) multiblock copolymers at various hydrophobic-hydrophilic ratios were successfully synthesized by the chain extension of triblock copolymers through isocyanate (hexamethylene diisocyanate). Biodegradable films were prepared from the resulting multiblock copolymers using the casting method. The mechanical properties of the films were improved by chain extension of the triblock copolymers, whereas the films prepared by the triblock copolymers were weak and brittle. Atomic force microscopy (AFM) of the multiblock copolymer film showed that the hydrophilic PEG had segregated on the film surface. This is consistent with the observed contact angle of the films.

• Korean Chemical Engineering Research
• /
• v.46 no.1
• /
• pp.15-22
• /
• 2008

Polyolefin block copolymer has been taking a great deal of attention due to their great potential in polymer industry since a new metallocene catalytic method for producing polyolefin block copolymer was developed by Dow Chemicals. However, so far, there was no systematic study of olefin block copolymer. In this review, Linear polyolefin block copolymers, containing semicrystalline poly (ethylene) (E) blocks and a rubbery block as a thermoplastic elastomer, were investigated in the viewpoint of microphase separation mode, microstructure, deformation behavior, and molecular architecture.

• Polymer Science and Technology
• /
• v.16 no.6
• /
• pp.754-768
• /
• 2005

• Polymer(Korea)
• /
• v.30 no.2
• /
• pp.152-157
• /
• 2006

Anionic or Zwitter-ionic waterbone polyurethanes (WPU) based on mixtures of hydroxy terminated poly-butadiene and poly(propylene glycol) were prepared and their physical properties were characterized. Particle size of WPU increased with increasing the content of HTPB. It was observed that the microphase separation of soft segments and hart segments increased with increasing the content of HTPB in the WPUs. Zwitter-ionic WPU showed stronger hydrogen bonds between molecules than anionic WPU after drying. Polyurethane films obtained after drying of WPUs exhibit besmechanical properties when the HTPB content among polyols for WPUs were 25wt%. It is postulated that such mechanical properties resulted from different microphase separation of soft segments and hard segments of polyurethane films obtainec after drying of WPUs.

• Bulletin of the Korean Chemical Society
• /
• v.16 no.9
• /
• pp.873-885
• /
• 1995

The local structural and thermodynamical properties of blends A-B/H of a diblock copolymer A-B and a homopolymer H are studied using the polymer reference interaction site model (RISM) integral equation theory with the mean-spherical approximation closure. The random phase approximation (RPA)-like static scattering function is derived and the interaction parameter is obtained to investigate the phase transition behaviors in A-B/H blends effectively. The dependences of the microscopic interaction parameter and the macrophase-microphase separation on temperature, molecular weight, block composition and segment size ratio of the diblock copolymer, density, and concentration of the added homopolymer, are investigated numerically within the framework of Gaussian chain statistics. The numerical calculations of site-site interchain pair correlation functions are performed to see the local structures for the model blends. The calculated phase diagrams for A-B/H blends from the polymer RISM theory are compared with results by the RPA model and transmission electron microscopy (TEM). Our extended formal version shows the different feature from RPA in the microscopic phase separation behavior, but shows the consistency with TEM qualitatively. Scaling relationships of scattering peak, interaction parameter, and temperature at the microphase separation are obtained for the molecular weight of diblock copolymer. They are compared with the recent data by small-angle neutron scattering measurements.

• Polymer(Korea)
• /
• v.25 no.3
• /
• pp.385-390
• /
• 2001

The A-B-A type block copoly(ester-ether)s consisting of poly(L-lactic acid) (PLLA)(A) and poly(oxyethylene-co-oxypropylene)(B) were prepared to improve the mechanical properties and hydrolyzability of PLLA. The block copolymers showed an improved flexibility due to the incorporation of the soft segments. Then, the same copolymer has an improved anti-thrombogenicity probably due to the specific microphase separation structure in the surface. The AFM of the film of the block copolymer revealed that the surface was quite flat in comparison with that of PLLA. Therefore, the flatness of the surface may be related with the increased anti-thrombogenicity of the copolymer film.

• Polymer(Korea)
• /
• v.28 no.6
• /
• pp.509-518
• /
• 2004

Microdomain structures and crystallization behavior of the binary blends consisting of an asymmetric block copolymer and a homopolymer were investigated using small-angle X-ray scattering (SAXS), optical micro scope (OM) and differential scanning calorimetry (DSC). Poly(methyl methacrylate)-block-polystyrene block copolymer (PMMA-b-PS) (weight fraction of PMMA =0.53) was mixed with low molecular weight poly(vinylidene fluoride) (PVDF). As the PVDF concentration was increased, the morphological change from a lamellar to a cylindrical structure occurred. The crystallization of PVDF significantly disturbed the orientation of the pre-existing microdomain structure, resulting in a poorly ordered morphology. In the blends, PVDF exhibited unique crystallization behavior due to the PMMA block which is preferentially miscible to PVDF and the space constraint imposed by the microdomains.

• Macromolecular Research
• /
• v.16 no.2
• /
• pp.113-119
• /
• 2008

A series of amphiphilic dendrons n-18 (n: generation number, 18: octadecyl chain) based on an aliphatic polyether denderitic core and octadecyl peripheries were synthesized using a convergent dendron synthesis consisting of a Williamson etherification and hydroboration/oxidation reactions. This study investigated their thermal and self-assembling behavior in the solid state using differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) absorption spectroscopy, and small angle X-ray scattering (SAXS). DSC indicated that the melting transition and the corresponding heat of the fusion of the octadecyl chain decreased with each generation. FT-IR showed that the hydroxyl focal groups were hydrogen-bonded with one another in the solid state. DSC and FT-IR indicated microphase-separation between the hydrophilic dendritic cores and hydrophobic octadecyl peripheries. SAXS data analysis in the solid state suggested that the lower-generation dendrons 1-18 and 2-18 self-assemble into lamellar structures based upon a bilayered packing of octadecyl peripheries. In contrast, the analyzed data of higher-generation dendron 3-18 is consistent with 2-D oblique columnar structures, which presumably consist of elliptical cross sections. The data obtained could be rationalized by microphase-separation between the hydrophilic dendritic core and hydrophobic octadecyl peripheries, and the degree of interfacial curvature associated with dendron generation.

• Korean Chemical Engineering Research
• /
• v.57 no.3
• /
• pp.392-399
• /
• 2019

A highly transparent interfacial layer (HTIL) to enhance the performance of dye-sensitized solar cells (DSSCs) was prepared via a polymer-assisted (PA) approach. Poly(vinyl chloride)-graft-poly(oxyethylene methacrylate) (PVC-g-POEM) was synthesized via atom-transfer radical polymerization (ATRP) and was used as a sacrificial template. The PVC-g-POEM graft copolymer induced partial coordination of a hydrophilic titanium isopropoxide (TTIP) sol-gel solution with the POEM domain, resulting in microphase separation, and in turn, the generation of mesopores upon calcination. These phenomena were confirmed using Fourier-transform infrared (FT-IR) spectroscopy, UV-visible light transmittance spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD) analysis. The DSSCs incorporating HTIL60/20 (consisting of a top layer with a pore size of 60 nm and a bottom layer with a pore size of 20 nm) exhibited the best overall conversion efficiency (6.36%) among the tested samples, which was 25.9% higher than that of a conventional blocking layer (BL). DSSC was further characterized using the Nyquist plot and incident-photon to electron conversion efficiency (IPCE) spectra.