• Bulletin of the Korean Chemical Society
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• v.9 no.1
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• pp.44-48
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• 1988

The feasibility of the reduction of nortricyclanone (1) as a chemical probe for testing the proposed radical mechanism for NAD-dependent horse liver alcohol dehydrogenase (HLADH) reactions has been examined using computer graphics modeling. The resutls of this study suggest that the radical ring-opening of this probe molecule may involve too substantial a geometry reorganization for the molecule to serve as a chemical probe in detecting the possible presence of the radical intermediates in the HLADH reactions. This result suggests that one should exercise caution in extrapolating results obtained from chemically based radical probes in the solution phase to the topologically constrained systems such as enzyme-substrate reactions.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.680-685
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• 1998

Two kinds of new aliphatic diols were synthesized by the ring-opening reaction of lactide and glycolide with 1,4-butanediol, a difunctional initiator, in the presence of stannous octoate. The resulting aliphatic diols were melt-polymerized with D-tartaric acid at 150 ℃ to produce new crosslinkable polyesters. They were reacted with hexamethylene diisocyanate in THF at 65 ℃ in a teflon mold for 24 h to prepare sequentially ordered crosslinked polyesters (BD/LT/GL/D-tartarate). Degradation of the prepared yellow crosslinked films was carried out in a buffer solution in order to examine the effect of time, pH, temperature and crosslinking degree on their degradation rate and mechanism. The rate of degradation increased with an increase in pH and temperature, but it decreased with increasing degree of crosslinkage incorporated into the crosslinked polyesters. We also found that the crosslinked polymers were converted into the acidic compounds such as lactic, glycolic, and D-tartaric acids during the degradation.

• Proceedings of the KSR Conference
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• 2008.11b
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• pp.1668-1673
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• 2008

고분자 복합재 구조물의 경우 일반적으로 여러 층의 단층(laminar)이 적층된 구조로 이루어져 있으며, 모재균열, 층간분리 및 섬유파단과 같은 손상이 발생되어 파단에 이르게 된다. 자가손상 복구기법은 복합소재의 열경화성 수지 내에 손상복구액을 포함하고 있는 마이크로캡슐과 촉매를 투입하여 외부의 도움 없이 손상을 치료할 수 있는 방법으로, 소재의 디자인에 있어서 새로운 페러다임을 제공할 수 있는 것으로 현재 많은 연구가 진행되고 있다. 본 연구에서는 ENB(5-ethylidene-2-norbornene)와 DCPD(dicyclopentadiene)에 대하여 DMA(dynamic mechanical analysis)와 DSC(differential scanning calorimetry)를 이용하여 특성을 분석하였다. 또한 그들의 ROMP(ring-opening metathesis polymerization)반응과의 관계를 조사하였으며, ENB와 DCPD 블렌드에 대한 복구액으로서의 특성도 조사하였다. 본 연구실에서 합성된 두 가지 다른 종류의 ROMP 경화제에 대한 실제 자가손상복구에으로서의 적용상 특성도 연구하였다.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.328-332
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• 1998

Anionic ring-opening polymerization of 3,4-[(dimethylsilyl)isopropyl]benzo-1,1-dimethyl-1-silacyclopentene in the presence of n-butyllithium and HMPA in THF at - 78 ℃ afforded poly[3,4-(dimethylsilylisopropyl)benzo-1,1-dimethyl-1-silapentene]. The characteristic Si-H stretching frequency in the IR is observed at 2100 cm-1. The polycarbosilane has been modified by chloroplatinic acid catalyzed addition of styrene to the polycarbosilane SiH units. Molecular weights and thermal properties of the polymers were compared. The sol-gel polymerization of 3,4-[(dimethoxysilyl)isopropyl]benzo-1,1-dimethoxy-1-silacyclopentene in the presence of aqueous HCl or NaOH in THF resulted in a cross-linked polysiloxane. The xerogel has a low surface area of 13-14 m2/g and is stable up to about 400 ℃ with only 5% weight loss under a nitrogen atmosphere.

• Polymer(Korea)
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• v.39 no.3
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• pp.506-513
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• 2015

Ethylidene norbornene (ENB) and its blends with endo-dicyclopentadiene (endo-DCPD) were prepared and reacted via the ring-opening metathesis polymerization (ROMP) reaction with the $1^{st}$ and $2^{nd}$ generation Grubbs' catalysts. Dynamic exothermic behaviors during ROMP and tensile properties after ROMP were evaluated using a differential scanning calorimeter (DSC) and a universal testing machine (UTM) for the samples, respectively. It revealed that the ROMP rate was accelerated with the less contents of endo-DCPD and under the $2^{nd}$ generation catalyst. Also, the addition of endo-DCPD and the $1^{st}$ generation catalyst resulted in higher tensile modulus and strength but lower toughness. Gel fraction measurement and fracture surface observation were made to understand the tensile properties.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2342-2348
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• 2014

Poly(lactic-co-glycolic acid) (PLGA) were grafted to both ends of Pluronic$^{(R)}$ F68 ($(EO)_{75}(PO)_{30}(EO)_{75}$) triblock copolymer to produce poly{(lactic acid)$_m$-co-(glycolic acid)$_n$}-b-poly(ethylene oxide)$_{75}$-b-poly(propylene oxide)$_{30}$-b-poly(ethylene oxide)$_{75}$-b-poly{(lactic acid)$_m$-co-(glycolic acid)$_n$} (PLGA-F68-PLGA) pentablock copolymers. Molecular weights of PLGA blocks were controlled and five kinds of pentablock copolymers with different PLGA block lengths were synthesized using in-situ ring-opening polymerization of D,L-lactide and glycolide with tin(II) 2-ethylhexanoate ($Sn(Oct)_2$) catalyst. PLGA-F68-PLGA pentablock copolymers were characterized by $^1H$- and $^{13}C$-NMR, GPC, and TGA. The numbers (2m, 2n) of repeating units for lactic acid and glycolic acid inside PLGA segments were obtained as (48, 17), (90, 23), (125, 40), (180, 59), and (246, 64), with $^1H$-NMR measurement. From NMR data, the resultant molecular weights were determined in the range of 12,700-29,700, which were similar to those obtained from GPC. Polydispersity index was increased in the range of 1.32-1.91 as the content of PLGA blocks increased. TG and DTG thermograms showed discrete degradation traces for PLGA and F68 blocks, which indicate the weight fractions of PLGA blocks in pentablock copolymers can be calculated by TG profile and it is possible to remove PLGA block selectively. Hydrodynamic radius and radius of gyration of pentablock copolymer micelle were obtained in the range of 46-68 nm and 31-49 nm, respectively, in very dilute (i.e. 0.005 wt %) aqueous solution of THF:$H_2O$ = 10:90 by volume at $25^{\circ}C$.

• 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.

• Polymer(Korea)
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• v.35 no.1
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• pp.52-59
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• 2011

L-PLA or D-PLA was synthesized in bulk at $140^{\circ}C$ by ring opening polymerization(ROP) of L-lactide or D-lactide as a monomer using tin(II) octoate and lauryl alcohol as a catalyst and an initiator with changing the amounts of catalyst(0.25~1.0 wt%) and initiator(0.l~0.5 wt%). And stereocomplex-PLA was prepared by L-PLA/D-PLA having a wide range of molecular weight(30000~90000 g/mol) and L-PLA/D-PLA blends having different mixing ratio ($X_D$). The melting temperature. thermal degradation temperature and thermal stability of stereocomplex-PLA were higher than those of homopolymers(L-PLA, D-PLA). We supposed that these improvements arose from a strong interaction between L-PLA and D-PLA. The improved mechanical properties and changes in morphology of LPLA/D-PLA blends were compared to those of homopolymers(L-PLA, D-PLA).

• Journal of Adhesion and Interface
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• v.16 no.4
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• pp.146-151
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• 2015

Raw sap of essential oil in Korean Dendropanax lacquer was extracted with ethanol, and which was cured by using ROMP (ring opening metathesis polymerization, one of olefin metathesis). Curing behavior with subsequent film properties were studied and compared with conventional curing (under ambient conditions) and UV photo curing. The compositional changes of major ingredients in the lacquer before and after curing were studied by using GC-MS (gas chromatography mass spectrometry). ROMP-cured coating film showed higher gel contents (40%) as compared to those of conventional (8%) and UV curing (25%). ROMP curing with 2 wt% Grubbs' catalyst at $100^{\circ}C$ completed curing reaction within 2 h, which was much faster than that of conventional curing. The quality of coating film prepared with ROMP was more homogeneous and wrinkle-free as compared with that with UV curing. It was found that major ingredients of sesquiterpenes, such as ${\alpha}$-selinene, ${\beta}$-selinene, and ${\delta}$-cadinene were reacted in ROMP, as well as polyacetylenes.

• Polymer(Korea)
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• v.38 no.1
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• pp.31-37
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• 2014

To prepare biomass based nylon 6,5 copolymers, ${\varepsilon}$-caprolactam and 2-piperidone, the monomers of nylon 6,5 copolymers, were synthesized respectively from lysine and 5-aminovaleric acid which were produced from glucose by the fermentation process. The copolymers were then polymerized by the anionic ring opening polymerization of them at $40^{\circ}C$, using potassium tert-butoxide as a catalyst and acetyl-2-caprolactam and carbon dioxide as initiators. The prepared copolymers were characterized with various analytical methods: their viscosity molecular weight ($M_{\eta}$) was as high as 30000 g/mol and polymerization yield was over 50%, and it was found that they were semi-crystalline polymers having melting point at $165^{\circ}C$ which was much lower than its thermal degradation point, $250^{\circ}C$. These polymers were expected to have good thermal processability and application fields.