• Macromolecular Research
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• 제16권8호
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• pp.704-710
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• 2008

Injectable hydrogels are quite promising materials due to their potential to minimize invasive implantation and this provides versatile fitness irrespective of the damaged regions and facilitates the incorporation of bioactive agents or cells. In situ gel formation through stereocomplex formation is a promising candidate for injectable hydrogels. In this paper, a new series of enantiomeric, four-arm, PEG-PLA block copolymers and their stereocomplexed hydrogels were prepared by bulk ring-opening polymerization of D-lactide and L-lactide, respectively, with stannous octoate as a catalyst. The prepared polymers were characterized by $^1H$ nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT IR) spectroscopy, gel permeation chromatography (GPC) and thermal gravitational analysis (TGA), confirming the tailored structure and chain lengths. The swelling and degradation behavior of the hydrogels formed from a selected copolymer series were observed in different concentrations. The degradation rate decreased with increasing polymer content in the solution. The rheological behavior indicated that the prepared hydrogel underwent in situ gelation and had favorable mechanical strength. In addition, its feasibility as an injectable scaffold was evaluated using a media dependence test for cell culture. A Tris solution was more favorable for in situ gel formation than PBS and DMEM solutions were. These results demonstrated the in situ formation of hydrogel through the construction of a stereocomplex with enantiomeric, 4-arm, PEG-PLA copolymers. Overall, enantiomeric, 4-arm, PEG-PLA copolymers are a new species of stereocomplexed hydrogels that are suitable for further research into injectable hydrogels.

• 한국환경과학회지
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• 제23권3호
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• pp.473-481
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• 2014

Poly(lactide)s(PLA) is an attractive material to solve the problem of waste plastic accumulation in nature because of its biodegradability. The lactide exists in three stereoisomeric configurations: L-lactide, D-lactide, and meso-lactide. PLA stereocomplexes, formed by the mixing of two enantiomers, poly(L-lactide)(PLLA) and poly(D-lactide)(PDLA), have many favorable characteristics because the stereocomplex showed $50^{\circ}C$ higher melting point than each enantiomeric polymer and the resistance toward degradation increased. In this study, we investigated the influence of the composition and the optical purity of each component on the formation of stereocomplexes. Also, the nanofibers of stereochemical PLA and their blends were prepared by electrospinning method. The properties of the obtained fibers were analyzed by differential scanning calorimetry and scanning electron microscopy. The results showed that a degree of stereocomplex was controlled by change of optical purity of each component. The enzymatic degradation of the fibers were strongly dependent on the stereocomplex.

• 한국산학기술학회논문지
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• 제13권2호
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• pp.919-925
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• 2012

광학 이성질체인 PLLA와 PDLA를 전 조성에서 블렌드하여 PLA stereocomplex(SC)를 제조하였고 DSC를 통해 PLLA matrix안의 SC결정 형성 정도를 파악하였다. 결과적으로 PLA SC blend의 PDLA 함량이 SC 결정 생성 정도에 영향을 주며 PLLA/PDLA=50/50의 조성일 때 가장 많은 SC 결정이 생성되었다. 더 나아가 고유의 낮은 충격강도를 보강하기 위하여 PLLA/PDLA=92/8, 85/15 조성에서 충격보강제(Impact modifiers)를 도입하였다. 제조된 PLA SC/Impact modifiers의 열적기계적 성질은 DSC, HDT, Izod Impact tester, UTM을 통해 측정하였다. DSC 측정 결과 PLA SC 결정은 Strong120(Impact modifier)가 10-20wt% 도입되면 감소하는 경향을 보이나 반면에 Elvaloy가 도입될 때에는 아무런 영향을 주지 않는 것으로 관찰되었다. HDT의 값은 PDLA의 도입에 따라 급격하게 $100^{\circ}C$이상으로 증가하였다. 하지만 Strong120과 Elvaloy가 도입됨에 따라 감소하는 경향을 보였다. 결국 Toughening된 PLA SC에서 10wt%의 Impact modifier를 blend하여 가장 최적의 충격강도와 굴곡탄성율을 갖는 물성을 발견할 수 있었다.

• 폴리머
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• 제39권3호
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• pp.453-460
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• 2015

초임계 유체 기술을 이용한 폴리락티드 스테레오 콤플렉스 제조는 폴리락티드의 열적 및 기계적 물성을 향상시키는 좋은 방법이다. 이 연구에서는 초임계 유체인 디메틸에테르를 이용하여 고분자량 폴리락티드를 높은 수율로 100% 스테레오 콤플렉스화를 시켰다. 폴리락티드에 대한 디메틸에테르의 높은 용해성은 이 공정의 핵심요소로 250 bar, $70^{\circ}C$, 1.5시간에 반응이 종료되었다. 폴리락티드의 스테레오 콤플렉스 연구는 압력, 온도, 시간, 농도 및 분자량을 변화시키며 진행하였다. 스테레오 콤플렉스화는 온도와 압력이 증가할 때 높아졌다. 분자량 20만 이상인 PLLA와 PDLA는 6%의 디메틸에테르에서 100% 스테레오 콤플렉스화가 이루어졌다. 스테레오 콤플렉스화 정도는 DSC 및 XRD를 통해 이루어졌다. 또한 DSC 및 TGA 분석을 통해 융점이 $50^{\circ}C$ 이상 높아진 폴리락티드가 얻어졌음을 확인하였다.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.52-53
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• 2006

A new series of PEO-PPO-PEO and PPO-PEO-PPO copolymers having several hydroxyl groups on the PPO chain segment were synthesized, further modified with various poly(lactic acid) PLA oligomeric chains to confer physical stability after thermo-gelation in the body fluid. Gel stability was endowed by either increasing hydrophobic interaction between PLA chains or inducing stereocomplex formation between enatiomeric isomers of PLA chains. Macromolecular drugs were incorporated within the gels and their release patterns were investigated using Pluronic F127 as a control.