• Macromolecular Research
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• v.11 no.6
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• pp.410-417
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• 2003

Poly(methyl methacrylate-co-acrylonitrile) [P(MMA-co-AN)]/Na-MMT nanocomposites were synthesized through emulsion polymerization with pristine Na-MMT. The nanocomposites were exfoliated up to 20 wt% content of pristine Na-MMT relative to the amount of MMA and AN, and exhibited enhanced storage moduli, E', relative to the neat copolymer. The exfoliated morphology of the nanocomposite was confirmed by XRD and TEM. 2-Acryla-mido-2-methyl-1-propane sulfonic acid (AMPS) widened the galleries between the clay layers before polymerization and facilitated the comonomers, penetration into the clay to create the exfoliated nanocomposites. The onset of the thermal decomposition of the nanocomposites shifted to a higher temperature as the clay content increased. By calculating areas of tan$\delta$ of the nanocomposites, we observed that the nanocomposites show more solid-like behavior as the clay content increases. The dynamic storage modulus and complex viscosity increased with clay content. The complex viscosity showed shear-thinning behavior as the clay content increased. The Young's moduli of the nano-composites are higher than that of the neat copolymer and they increase steadily as the silicate content increases, as a result of the exfoliated structure at high clay content.

• Macromolecular Research
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• v.15 no.4
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• pp.308-314
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• 2007

The effects of a compatibilizer on polypropylene (PP)/poly(acrylonitrile-butadiene-styrene) (ABS) blends were studied. Blends of the PP/ABS, with PP-g-SAN copolymer as a compatibilizer, were prepared using a twin screw extruder. The flexural and impact strength of the PP/ABS blends with the PP-g-SAN copolymer increased significantly with PP-rich compositions on the addition of the PP-g-SAN copolymer at 3 phr. The increase in the mechanical properties of the PP/ABS/PP-g-SAN blend may have been due to the toughening effects of the ABS in the PP-rich compositions. In the morphology study of the PP/ABS/PP-g-SAN (80/20) blend with the PP-g-SAN copolymer, the minimum droplet size, $5.1{\mu}m$, was observed with the addition on phr of the PP-g-SAN copolymer. The complex viscosity of the PP/ABS/PP-g-SAN (80/20) blends increased with the addition of3 phr of the PP-g-SAN copolymer. From the above mechanical properties, morphology and complex viscosity results for the PP/ABS blends, it is suggested that the compatibility is more increased with the PP-rich composition (PP:ABS=80/20 wt%) of the PP/ABS blend on the addition of 3 phr of the PP-g-SAN copolymer.

• Macromolecular Research
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• v.15 no.6
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• pp.520-526
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• 2007

The effects of poly($({\varepsilon}$-caprolactone) (PCL) on poly(acrylonitrile-butadiene-styrene) (ABS) and polycarbonate (PC) blends were studied. Blends of ABS/PC (70/30, wt%) with PCL as a compatibilizer were prepared by a twin screw extruder. From the glass transition temperature $(T_g)$ results of the ABS/PC blends with PCL, the $T_g$(PC) of the ABS/PC (70/30) blends decreased with increasing PCL content. From the results of the morphology of the ABS/PC (70/30) blends with PCL, the phase separation between the ABS and PC phases became less significant after adding PCL in the ABS/PC blends. In addition, the morphological studies of the ABS/PC blends etched by NaOH indicated that the shape of the droplet was changed from regular round to irregular round by adding PCL in the ABS/PC blends. These results for the mechanical properties of the ABS/PC blends with PCL indicated that the tensile, flexural and impact strengths of the ABS/PC (70/30) blends peaked at a PCL content of 0.5 phr. From the results for the rheological properties of the ABS/PC (70/30) blends with PCL content, the storage modulus, loss modulus and complex viscosity increased at PCL content up to 5 phr. From the above results of the $T_g$, mechanical properties, morphology and complex viscosity of the ABS/PC blends with PCL, it was concluded that the compatibility was increased with PCL addition in the ABS/PC (70/30, wt%) blends and that the optimum concentration of PCL as a compatibilizer is 0.5 phr.

• Macromolecular Research
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• v.17 no.2
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• pp.110-115
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• 2009

The electrical, morphological and rheological properties of melt and dry mixed composites of poly ethylene (PE)/graphite (Gr), polypropylene (PP)/Gr and PP/nickel-coated carbon fiber (NCCF) were investigated as a function of filler type, filler content and processing temperature. The electrical conductivities of dry mixed PP/NCCF composites were increased with decreasing processing temperature. For the melt mixed PP/NCCF composites, the electrical conductivities were higher than those of the melt mixed PE/Gr and PP/Gr composites, which was attributed to the effect of the higher NCCF aspect ratio in allowing the composites to form a more conductive network in the polymer matrix than the graphite does. From the results of morphological studies, the fillers in the dry mixed PP/NCCF composites were more randomly dispersed compared to those in the melt mixed PP/NCCF composites. The increased electrical conductivities of the dry mixed composites were attributed to the more random dispersion of NCCF compared to that of the melt mixed PP/NCCF composites. The complex viscosities of the PP/Gr composites were higher than those of the PP/NCCF composites, which was attributed to the larger diameter of the graphite particles than that of the NCCF. Furthermore, the fiber orientation in the 'along the flow' direction during melt mixing was attributed to the decreased complex viscosities of the melt mixed PP/NCCF composites compared those of the melt mixed PP/Gr composites.

• Macromolecular Research
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• v.11 no.5
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• pp.375-381
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• 2003

Silver salt complex membranes with glassy poly(methyl methacrylate) (PMMA) unexpectedly showed higher propylene permeance than those with rubbery poly(butyl methacrylate) (PBMA) where as neat PMMA is much less permeable to propylene than that of neat PBMA. Such unusual facilitated olefin transport has been systematically investigated by changing the side chain length of polymethacrylates (PMAs) from methyl, ethyl to butyl. The ab initio calculation showed almost the same electron densities of the carbonyl oxygens in the three PMAs, expecting very similar intensity of the interaction between carbonyl oxygen and silver ion. However, the interaction intensity decreases with the length of the alkyl side chain: PMMA > PEMA > PBMA according to wide angle X-ray scattering and FT-Raman spectroscopy. The difference in the interaction intensity may arise from the difference in the hydrophilicity of the three PMAs, as confirmed by the contact angle of water, which determines the concentrations of the ionic constituents of silver salts: free ion, contact ion pair and higher order ionic aggregate. However, propylene solubilities and facilitated propylene transport vary with the side chain length significantly even at the same concentration of the free ion, the most active olefin carrier, suggesting possible difference in the prohibition of the molecular access of propylene to silver ion by the side chains: the steric hindrance. Therefore, it may be concluded that both the hydrophilicity and the steric hindrance associated with the side chain length in the three PMAs are of pivotal importance in determining facilitated olefin transport through polymer/silver salt complex membranes.

• Macromolecular Research
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• v.12 no.2
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• pp.195-205
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• 2004

We have synthesized new aromatic polyesters (DiPEG-HQ and DiPEG-BP) by condensation polymerization of a terephthalic acid derivative bearing a pendant oligo(oxyethylene) (DP = 7, MW = 350), which has a methoxy terminal group, and two different aromatic diols, hydroquinone and 4,4'-biphenoI. The synthesized polymers were characterized by differential scanning calorimetry (DSC), polarizing microscopy, and X-ray diffractometry for their liquid crystallinity (LC), thermal transitions, and structural morphologies in mesophases. The morphology of the LC phases depends strongly on the length of the rigid backbone repeating unit. The DiPEG-BP polymer having a longer repeating unit exhibits both layered and nematic structures before isotropization, whereas the DiPEG-HQ polymer having a shorter repeating unit shows only the layered structure in the mesophase. We found that the layer spacing for DiPEG-HQ is larger than that for DiPEG-BP. Both polymers easily form complexes with LiCF$_3$SO$_3$; we studied this complex formation by FT-IR spectroscopy. The layer spacing of the polymer-electrolyte composites increases upon increasing the amount of the lithium salt. The polymer/salt electrolyte mixtures we investigated at molar ratios of EO:salt in the range of 5-20 exhibit electrical conductivity values at 40$^{\circ}C$ of 2.4${\times}$10$\^$5/ and 1.1${\times}$10$\^$－5/ S/cm for DiPEG-HQ/LiCF$_3$SO$_3$ and DiPEG-BP/LiCF$_3$SO$_3$, respectively. At 80 $^{\circ}C$, these values are higher: 4.6${\times}$10$\^$－3/ and 1.1${\times}$10$\^$－4/ S/cm, respectively. The activation energy of conductivity depends strongly on the salt concentration.

• Macromolecular Research
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• v.14 no.5
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• pp.573-578
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• 2006

Three different, polymer-platinum conjugates (hydrogels, microparticles, and nanoparticles) were synthesized by complexation of cis-dichlorodiammineplatinum(II) (cisplatin) with partially succinylated glycol chitbsan (PSGC). Succinic anhydride was used as a linker to introduce cisplatin to glycol chitosan (GC). Succinylation of GC was investigated systematically as a function of the molar ratio of succinic anhydride to glucosamine, the methanol content in the reaction media, and the reaction temperature. By controlling the reaction conditions, water-soluble, partially water-soluble, and hydrogel-forming PSGCs were synthesized, and then conjugated with cisplatin. The complexation of cisplatin with water-soluble PSGC via a ligand exchange reaction of platinum from chloride to the carboxylates induced the formation of nano-sized aggregates in aqueous media. The hydrodynamic diameters of PSGC/cisplatin complex nano-aggregates, as determined by light scattering, were 180-300 nm and the critical aggregation concentrations (CACs), as determined by a fluorescence technique using pyrene as a probe, were $20-30{\mu}g/mL$. The conjugation of cisplatin with partially water-soluble PSGC, i.e., borderline between water-soluble and water-insoluble PSGC, produced micro-sized particles $<500{\mu}m$. Cisplatin-complexed PSGC hydrogels were prepared from water-insoluble PSGCs. All of the cisplatin-incorporated, polymer matrices released platinum in a sustained manner without any significant initial burst, suggesting that they may all be useful as slow release systems for cisplatin. The release rate of platinum increased with the morphology changes from hydrogel through microparticle to nanoparticle systems.

• Macromolecular Research
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• v.14 no.5
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• pp.530-538
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• 2006

There are three important components in tissue engineering: the cells, signaling factors (cytokines and growth factors), and scaffolds. To obtain finely engineered tissue, all three components should perform their individual functions and be fully integrated with each other. For the past few years, we have studied the characteristics of photodimerizable HA (CHA)/alginate (CA) composite materials. CHA/CA complex hydrogels, which were irradiated under UV light and, then treated with calcium ions, were found to have good biocompatibility, mechanical properties and water resistance for implantable tissue scaffolds. In this study, we introduced a cell growth factor (basic fibroblast growth factor; bFGF) into the CHA/CA scaffolds and studied its release behavior. We also introduced tetracycline hydrochloride and flurbiprofen into the same scaffolds as model activation factors and evaluated their release behaviors from the scaffolds. The drug release rate from the materials was influenced by various parameters, such as the degree of crosslinking, the cross linker type, the physico-chemical properties of the drug, and the amount of the drug in the polymer. The results indicated that the negatively charged CHA/CA composite materials showed sustained release behavior and that HA has a particularly strong negative charge, making it attractive toward tetracycline hydrochloride and bFGF, but repulsive toward flurbiprofen.

• Macromolecular Research
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• v.12 no.4
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• pp.422-426
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• 2004

Solid polymer electrolytes based on poly(ethylene glycol)-polyurethane (PEG-PU) complexed with LiClO$_4$ salt have been prepared by the solvent casting method. A PEG-PU material (PEG:4,4'-diphenylmethane diisocyanate: l,4-butanediol = 1:2:1) was synthesized through a typical two-step condensation reaction. We investigated the effects of the salt concentration on the ionic conductivity ($\sigma$) and the glass transition temperature (T$_{g}$ ) of the complex electrolytes by using alternating current impedance spectroscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The measured values of both $\sigma$ and T$_{g}$ exhibited similar tendencies in that they had maxima within the range studied, probably because of two opposite effects, i.e., the increased number of carrier ions and the decreased chain mobility (or increased T$_{g}$ ) caused by the increase in the salt concentration. The highest conductivity, on the order of 2.43 ${\times}$ 10$^{6}$ S$cm^{-1}$ /, was obtained at an [O]/[Li$^{+}$] ratio of ca. 16 (0.92 ㏖ salt per kg of matrix polymer).

• Macromolecular Research
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• v.17 no.11
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• pp.863-869
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• 2009

The effect of a multiwalled carbon nanotube (MWCNT) dispersion on the electrical, morphological and rheological properties of polycarbonate (PC)/MWCNT composites was investigated, with and without pretreating the MWCNTs with hydrogen peroxide oxidation and lyophilization. The resulting PC/treated MWCNT composites showed higher electrical conductivity than the PC/untreated MWCNT composites. The morphological behavior indicated the treated composites to have greater dispersion of MWCNTs in the PC matrix. In addition, the electromagnetic interference shielding efficiency (EMI SE) of the treated composites was higher than that of the untreated ones. Rheological studies of the composites showed that the complex viscosity of the treated composites was higher than the untreated ones due to increased dispersion of the MWCNTs in the PC matrix, which is consistent with the electrical conductivity, EMI SE and morphological studies of the treated composites. The latter results suggested that the increased electrical conductivity and EMI SE of the treated composites were mainly due to the increased dispersion of MWCNTs in the PC matrix.