• Macromolecular Research
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• v.16 no.1
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• pp.66-69
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• 2008

• Proceedings of the Optical Society of Korea Conference
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• 2006.07a
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• pp.485-486
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• 2006

• Polymer Science and Technology
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• v.16 no.6
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• pp.799-806
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• 2005

• Polymer Science and Technology
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• v.10 no.4
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• pp.485-492
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• 1999

• Applied Chemistry for Engineering
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• v.25 no.2
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• pp.121-133
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• 2014

Block copolymers including ABA triblock architectures are useful as thermoplastic elastomers and toughened plastics depending on the relative glassy and rubbery content. These materials can be blended with other polymers and utilized as additives, toughening agents, and compatibilizers. Most of commercially available block copolymers are derived from petroleum. Renewable alternatives are attractive considering the finite supply of fossil resources on earth and the overall economic and environmental expenses involved in the recovery and use of oil. Furthermore, tomorrow's sustainable materials are demanding the design and implementation with programmed end-of-life. The present review focuses on the preparation and evaluation of new classes of renewable ABA triblock copolymers and also emphasizes on the use of carbohydrate-derived poly(lactide) or plant-based poly(olefins) having a high glass transition temperature and/or high melting temperature for the hard phase in addition to the use of bio-based amorphous hydrocarbon polymers with a low glass transition temperature for the soft components. The combination of multiple controlled polymerizations has proven to be a powerful approach. Precision-controlled synthesis of these hybrid macromolecules has led to the development of new elastomers and tough plastics offering renewability, biodegradability, and high performance.

• Polymer(Korea)
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• v.33 no.2
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• pp.158-163
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• 2009

In this study, we synthesized a series of dendritic polystyrene-b-linear poly (t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene ($M_n$ = 1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly (t-butyl acrylate)s were prepared by an atom transfer radical polymerization (ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly (t-butyl acrylate) s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under $H_2$ atmosphere. In the final step, dendritic-linear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino) pyridine(DMAP) and N,N'-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by $^1H$-NMR spectroscopy and gel permeation chromatography(GPC).

• Macromolecular Research
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• v.12 no.1
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• pp.127-133
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• 2004

We have studied the surface micelle formation of polystyrene-b-poly(2-vinyl pyridine) (PS-b-P2VP) at the air-water interface. A series of four PS-b-P2VPs were synthesized by anionic polymerization, keeping the PS block length constant (28 kg/㏖) and varying the P2VP block length (1, 11, 28, or 59 kg/㏖). The surface pressure-area ($\pi$-A) isotherms were measured and the surface morphology was studied by atomic force microscopy (AFM) after Langmuir-Blodgett film deposition onto silicon wafers. At low surface pressure, the hydrophobic PS blocks aggregate to form pancake-like micelle cores and the hydrophilic P2VP block chains spread on the water surface to form a corona-like monolayer. The surface area occupied by a block copolymer is proportional to the molecular weight of the P2VP block and identical to the surface area occupied by a homo-P2VP. It indicates that the entire surface is covered by the P2VP monolayer and the PS micelle cores lie on the P2VP monolayer. As the surface pressure is increased, the $\pi$-A isotherm shows a transition region where the surface pressure does not change much with the film compression. In this transition region, which displays high compressibility, the P2VP blocks restructure from the monolayer and spread at the air-water interface. After the transition, the Langmuir film becomes much less compressible. In this high-surface-pressure regime, the PS cores cover practically the entire surface area, as observed by AFM and the limiting area of the film. All the diblock copolymers formed circular micelles, except for the block copolymer having a very short P2VP block (1 kg/㏖), which formed large, non-uniform PS aggregates. By mixing with the block copolymer having a longer P2VP block (11 kg/㏖), we observed rod-shaped micelles, which indicates that the morphology of the surfaces micelles can be controlled by adjusting the average composition of block copolymers.

• Polymer(Korea)
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• v.24 no.5
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• pp.664-672
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• 2000

It is generally agreed that transesterification provides the, copolymer in the melt blending of poly(ethylene naphthalate) (PEN) and poly($\varepsilon$-caprolactone) (PCL). Effects of the conditions of transesterification reaction and catalyst on the degree of randomness and average sequence length of PEN/PCL blends were investigated and results were used to interpret the biodegradability of PEN/PCL blends. It was found that degree of randomness values of obtained copolymer lied between 0 and 1, and it indicated that this blend consisted with physical blends of PEN/PCL and PEN/PCL block copolymers. The degree of randomness reached almost 1 which is the theoretical value of random copolymers and the average sequence length became shorter by the further transesterification reaction. In additions, it was found that the increase of copolymers, especially random copolymers reduced the biodegradability in PEN/PCL blends.

• Polymer(Korea)
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• v.28 no.4
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• pp.344-351
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• 2004

Poly(ethylene glycol)-based diblock and triblock polyester copolymers stimulating to temperature were studied as injectable biomaterials in drug delivery system because of their nontoxicity, biocompatibility and biodegradability. We synthesized the diblock copolymers consisting of methoxy poly(ethylene glycol) (MPEG) (M$_{n}$=750 g/mole) and poly($\varepsilon$-caprolactone) (PCL) by ring opening polymerization of $\varepsilon$-CL with MPEG as an initiator in the presence of HCl . Et$_2$O. The aqueous solution of synthesized diblock copolymers represented sol phase at room temperature and a sol to gel phase transition as the temperature increased from room temperature to body temperature. To confirm the in vivo gel formation, we observed the formation of gel in the mice body after injection of 20 wt% aqueous solution of each block copolymer. After 2 months, we observed the maintenance of gel without dispersion in mice. In this study, we synthesized diblock copolymers exhibiting sol-gel phase transition and confirmed the feasibility as biomaterials of injectable implantation.n.

• Polymer(Korea)
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• v.28 no.3
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• pp.232-238
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• 2004

MPEG-PCL diblock copolymers consisting of methoxy poly(ethylene glycol) (MPEG) and $\varepsilon$-caprolactone (CL) as drug carriers were synthesized by ring-opening polymerization MPEG-PCL diblock copolymers were characterized by X-ray diffraction and differential scanning calorimetry. After freeze milling of block copolymers and albumin bovine-fluorescein isothiocyanate (FITC-BSA) as model protein, the wafers loaded FITC-BSA were fabricated by direct compression method. The release profiles of FITC-BSA were examined using pH 7.4 PBS for 14 days at 37$^{\circ}C$. The release amount was determined by fluorescence intensity by using the fluorescence spectrophotometer. The morphological change of wafers was observed by digital camera and scanning electron microscope. The release rate and initial burst of BSA increased with increasing PEG molecular weights and decreasing PCL molecular weights in the segments of MPEG -PCL diblock copolymers.