• Polymer(Korea)
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• v.30 no.2
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• pp.146-151
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• 2006

Linear and branched copolymers consisting of poly(ethylene glycol) (PEG) and $Poly({\varepsilon}-caprolactone)$ (PCL) were prepared to compare the characterization of star-shaped copolymers with various molecular architecture. Linear and branched PEG-PCL (1-arm, 2-arm, 4-arm, and 8-arm) copolymers were synthesized by the ring-opening polymerization of ${\varepsilon}-caprolactone$ in the presence of HCl $Et_2O$ as a monomer activator at room temperature. The synthesized copolymers were characterized with $^1H-NMR$, GPC, DSC, and XRD. As a result of the DSC and XRD, each copolymers showed different thermal properties and crystallinity according to the number of ms. The micellar characterization of linear and branched copolymers in an aqueous phase was carried out by using NMR, dynamic light scattering, AM, and fluorescence techniques. The critical micelle concentration (CMC) and diameters of micelles depended on the number of arms. Most micelles exhibited a spherical shape in AFM. In this study, we characterized star-shaped PEG-PCL copolymers and investigated their molecular architecture effect on the various properties. Furthermore, we confirmed that the micelles termed with linear and branched PEG-PCL copolymers have possibility as a potential hydrophobic drug delivery vehicle.

• Applied Chemistry for Engineering
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• v.2 no.4
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• pp.348-355
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• 1991

Polysiloxane copolymers were prepared by copolymerizing hexamethylcyclotrisiloxane with tetramethylcyclotetrasiloxane, and then reacted with allyamine. Copolymers containing naphthoquinone-1,2-diazide-5-sulfonyl group were synthesized by reacting naphthoquinone-1,2-diazide-5-sulfonyl chloride with siloxane copolymers having amino group. Thermal decomposition temperatures of copolymers were $360{\sim}450^{\circ}C$, and photosensitive characteristics were dependent on the molecular weights of backbone resins and sensitizers. Sensitivity of copolymers was $50{\sim}120mJ/cm^2$ and contrast(${\gamma}$) was 1.4~2.1.

• Macromolecular Research
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• v.10 no.2
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• pp.85-90
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• 2002

Poly (ethylene oxide)/polylatide/poly(ethylene oxide) (PEO/PL/PEO) tri-block copolymers, which each block is connected by ester bond, were synthesized by coupling reaction of PL with PEO in the presence of pyridine. PL/PEO/PL tri-block copolymer was synthesized by ring opening polymerization of L-lactide initiated by PEO in the presence of stannous octoate. Degradation behavior of the copolymers was investigated in a pH 7.4 phosphate buffer saline (PBS) at 37$\pm$1 $^{\circ}C$. Gel permeation chromatography (GPC) and $^1$H-nuclear magnetic resonance (NMR) were used to monitor the change of mass loss, molecular weight and composition of copolymers. In hydrolytic degradation, the PEO/PL/PEO tri-block copolymer with high PEO contents affected the increase of its mass loss, and resulted in the decrease of its molecular weight as well as PEO composition. However, when PL/PEO/PL and PEO/PL/PEO tri-block copolymers had similar PEO contents, PEO/PL/PEO decreased faster in molecular weight and PEO composition than PL/PEO/PL.

• Journal of Information Display
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• v.5 no.4
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• pp.12-17
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• 2004

A series of statistical random copolymers of dioctylfluorene (DOF) and 3,4-ethylenedioxythiophene (EDOT) were synthesized by Ni (0) mediated polymerization and their light-emitting properties were compared with poly (9,9-di-n-octylfluorene) (PDOF). The synthesized polymers were characterized using UV-vis spectroscopy, TGA, photoluminescence (PL) & electroluminescence (EL) spectroscopy and by conducting molecular weight studies. The resulting polymers were found to be thermally stable and readily soluble in organic solvents. The UV-visible absorption and PL emission spectra of the copolymers were gradually red-shifted as the fraction of EDOT in copolymers increased. Light-emitting devices were fabricated in an ITO (indium-tin oxide)/PEDOT/polymer/Ca/Al configuration. Interestingly, the EL spectra of these devices were similar to the PL spectra of the corresponding polymer film. However, the EL devices constructed from the copolymer showed more than 10 times higher efficiency level than the devices constructed from the PDOF homopolymer. This higher efficiency is possibly the result of better charge carrier balance in the copolymer systems due to the lower HOMO levels of the copolymers in comparison to that of PDOF homopolymer.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2006.05a
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• pp.55-60
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• 2006

Thermally stable and solution-processable poly(N-arylcarbazole-alt-aniline) copolymers with high structural integrity were synthesized in good yields via palladium-catalyzed polycondensation of aniline with corresponding N-arylcarbazole monomers such as N-(2-ethylhexyloxyphenyl)-3,6-dibromocarbazole,bis[6-bromo-N-(2-ethylhexyloxyphenyl)carbazole-3-yl] and N-(4-(2-ethylhexyl)-3,5-dibromomethylene-phenyl) carbazole, respectively. The optical and electrochemical properties of these copolymers were measured and compared with those of poly(N-alkylcarbazole-alt-aniline) copolymer. All synthesized poly(N-arylcarbazole-alt-aniline) copolymers showed maximum UV-Vis absorption peaks at around 300 nm in THF solution, and exhibited maximum photoluminescence peaks in the blue emission range from 430 to 460 nm. It was also found that poly(N-arylcarbazole-alt-aniline) copolymers had wider band gap energy than poly(N-alkylcarbazole-alt-aniline) copolymer.

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.872-879
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• 2002

One of the improtant characteristics of core-shell type nanoparticles is the long-term storage and reuse as an aqueous injection solution when required. For this reason, reconstruction of lyophilized core-shell type nanoparticles is considered to be essential . BAB type triblock copolymers differ from AB type diblock copolymers, which contain the A block as a hydrophilic part and the B block as a hydrophobic part. by not being easily redistributed into phosphate-buffered saline (PBS, pH 7.4, 0.1 M). Therefore, lyophilized core-shell type nanoparticles of CEC triblock copolymer were reconstituted using a somication process with a bar-type sonicator in combination with a freezing-thawing process. Soncation for 30s only resuspended CEC nanoparticles in PBS; their particle size distribution showed a monomodal pattern with narrow size distribution. The bimodal size distribution pattern and the aggregates were reduced by further sonication for 120 s but these nanoparticles showed a wide size distribution. The initial burst of drug release was increased by reconstitution process. The reconstitution of CEC core-shell type nanoparticles by freezing-thawing resulted in trimodal distribution pattern and formed aggregates, although freezing-thawing process was easier than sonication . Drug release form CEC nanoparticles prepared by freezing-thawing was slower than from the original dialysis solution. Although core-shell typenanoparticles of CEC triblock copolymers were not easily performed. Cytotoxicity testing of core-shell type nanoparticles of CEC-2 triblock copolymers containing clonazepam (CNZ) was performed using L929 cells. Cytotoxicity of CNZ was decreased by incorporation into nanoparticles.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.76-80
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• 1995

Polydimethylsiloxane(PDMS)-co-poly(2-hydroxyethyl methacrylate)(PHEMA) was prepared and the degree of swelling of solvents into the polymers was examined. It was confirmed that the solubility parameter of PHEMA homopolymer is 26 (J/cm3)1/2. Ethanol was significantly absorbed into copolymers containing large amount of PHEMA, while tetrahydrofuran was effectively absorbed into copolymers containing large amount of PDMS. Absorption of polar solvents into the copolymers were increased with the increase of PDMS content. The model drug, crystal violet (CV), was more absorbable into PDMS-HPEMA copolymers than PHEMA homopolymer. Absorption of CV was decreased with the increase of PDMS content of the copolymers.

• Macromolecular Research
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• v.12 no.5
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• pp.459-465
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• 2004

We have synthesized poly(l,4-cyclohexylenedimethylene terephthalate-co-hexamethylene terephthalate) [P(CT-co-HT)] random copolymers having various comonomer contents, from 0 to 100 mol% HT, by melt-condensation and have investigated their crystallization behavior by using differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). We observed that P(CT-co-HT)s exhibit clear melting and crystallization peaks in their DSC thermograms and sharp diffraction peaks in their WAXD patterns for all of their copolymer compositions as a result of cocrystallization of the CT and HT units, even though the copolymers are statistically random copolymers. When we plotted the melting and crystallization temperatures of P(CT-co-HT)s and the d-spacings of all the reflections against the copolymer composition, we observed a eutectic point at ca. 80 mol% HT, which suggests that a crystal transition occured from a PCT-type crystal to a PHT-type crystal. Both the DSC and WAXD results support the notion that P(CT-co-HT) copolymers undergo an isodimorphic cocrystallization.

• Macromolecular Research
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• v.17 no.6
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• pp.365-377
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• 2009

In this feature article, we briefly review the new methods we have utilized recently in the investigation of morphology and phase behavior of block copolymers. We first describe the chromatographic fractionation method to purify block copolymers from their side products of mainly homopolymers or block copolymer precursors inadvertently terminated upon addition of the next monomer in the sequential anionic polymerization. The chromatographic method is extended to the fractionation of the individual block of diblock copolymers which can yield the diblock copolymer fractions of different composition and molecular weight, which also have narrower distributions in both molecular weight and composition. A more detailed phase diagram could be constructed from the set of block copolymer fractions without the need of acquiring many block copolymers each prepared by anionic polymerization. The fractions with narrow distribution in both molecular weight and composition exhibit better long-range ordering and sharper phase transition. Next, epitaxial relationships between two ordered structures in block copolymer thin film is discussed. We employed the direct visualization method, transmission electron microtomography(TEMT) to scrutinize the grain boundary structure.

• Macromolecular Research
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• v.16 no.7
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• pp.614-619
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• 2008

Copolymers of phenyl alkyl acrylates/methacrylates are used clinically as soft materials for the foldable intraocular lens (IOL) to treat cataracts. In this study, copolymers of 2-phenylethyl acrylate (PEA) and 2-phenylethyl methacrylate (PEMA) of various compositions were prepared using free radical polymerization in solution. The composition of the copolymers was determined by $^1H$-NMR analysis. The reactivity ratios of the monomers were calculated using the conventional Fineman-Ross or Kelen-Tudos method. The reactivity ratio of PEA ($r_1$) and PEMA ($r_2$) were estimated to be 0.280 and 2.085 using the Kelen-Tudos method, respectively. These values suggest that PEMA is more reactive in copolymerization than PEA, and the copolymers will have a higher content of PEMA units. The glass transition temperature ($T_g$) of the copolymers increased with increasing PEMA content. The molecular weight and polydispersity indices ($M_w/M_n$) of the polymers were determined by GPC. Overall, these results are expected to be quite useful in applications to foldable soft IOL materials.