• 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.24 no.5
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• pp.638-645
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• 2000

Linear and star-shaped, poly(lactic acid) (PLA) stereo-block copolymers were synthesized by sequential polymerization of DL-lactic acid and L-lactide in the presence of diol or polyol compounds. The molecular weight of block copolymers could be controlled to some extent by the variation of alcohol content. These block copolymers had relatively narrow molecular weight distributions. The glass transition temperature and melting temperature of block copolymers appeared at around 5$0^{\circ}C$ and 100~14$0^{\circ}C$, respectively. The block copolymers were found to crystallize even at the high D-stereoisomer concentration of 35 mol%, in contrast to the amorphous nature of the random copolymer with similar composition. Also we could observe the crystallinity of PLA stereo-block copolymers varying with annealing temperature and time.

• Polymer(Korea)
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• v.27 no.6
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• pp.528-535
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• 2003

The effects of surfactants, organic solvents, and functional monomers on the emulsion polymerization of perfluoroalkyleoylacryaltes and n-alkylacrylates were investigated. In particular, the dependence of the surface properties, contact angle and water repellency on the crystal melting temperature (T$\_$m/) of the fluorocopolymer and the variation of polymer latex particle sizes was investigated. Using WAXD experiments and synthesizing different types of fluorocopolymers which have fallowing fluoroacrylaytes [CH$_2$=CHCO$_2$CH,$_2$(CF$_2$CF$_2$) nH] (n = 4, 5 or 6), the relationship between the molecular packing structure of pendent side groups of fluorocopolymers and the surface properties was also investigated. We observed that the structure of primary carbon atoms of pendent side groups of fluorocopolymers plays key role in determining the surface properties.s.

• Korean Chemical Engineering Research
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• v.46 no.1
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• pp.1-6
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• 2008

Block copolymers spontaneously assemble into various nanoscale structures such as spheres, cylinders, and lamellar structures according to the relative volumn ratio of each macromolecular block and their overall molecular weights. The self-assembled structures of block copolymer have been extensively investigated for the applications such as nanocomposites, photonic crystals, nanowires, magnetic-storage media, flash memory devices. However, the naturally formed nanostructures of block copolymers contain a high density of defects such that the practical applications for nanoscale devices have been limited. For the practical application of block copolymer nanostructures, a robust process to direct the assembly of block copolymers in thin film geometry is required to be established. To exploit self-assembly of block copolymer for the nanotechnology, it is indispensible to fabricate defect-free self-assembled nanostructure over an arbitrarily large area.

• Elastomers and Composites
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• v.48 no.1
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• pp.30-38
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• 2013

Polyolefin is one of the most important commodity polymers having excellent physical properties and cost competitiveness, which has continuously broadened their market in response to a heavy demand from industry. However, the lack of polarity in polyolefin has limited its applications, especially where interactions with other materials are important. In view of the above, the incorporation of polar functional groups in polyolefin has been widely attempted. Especially, the preparations of segmented modified polyolefin copolymers, such as block and graft copolymers have been extensively investigated, since the loss of the original properties of polyolefin can be minimized while the polar segments can endow interactions with other materials. Living radical polymerization (LRP) method can be one of the most attractive synthetic tools for the preparation of the modified polyolefin block or graft copolymers. In this review, progress on the preparation of the polyolefin based block or graft copolymers through LRP technique is briefly summarized.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.440-444
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• 1998

Poly(phenylene sulfide-co-phenylene sulfide sulfone), PPS/PPSS copolymers were synthesized from p-dichlobenzene(DCB), p-dibromobenzene(DBB), p-diiodobenzene(DIB), 4-chlorophenyl sulfone(CPS) and sodium sulfide as comonomers under high temperature and pressure utilizing N-methyl-2-pyrrolidinone(NMP) as solvent. The yield of PPS/PPSS copolymer shoed maximum at $190^{\circ}C$ with [DBB]/[CPS] and [DIB]/[CPS] comonomer pair, while [DCB]/[CPS] pair exhibited maximum yield at $230^{\circ}C$. The change of yield is in the order of I>Br>Cl as leaving groups were in accordance with nucleophilic aromatic substitution reaction mechanism suggested for the synthesis of PPS type polymers. The molecular weight of PPS/PPSS copolymer was the highest($M_w=8,330g/mol$) with [DBB]/[CPS] comonomers in which [CPS] was 10 mole%. The PPS/PPSS copolymer made with 10 mole% of [CPS] showed about $15^{\circ}C$ higher $T_g$ and $15^{\circ}C$ lower $T_m$ than those of PPS homopolymer, which may be useful from the processing and thermal property point of view. The PPS/PPSS copolymer with 30 mole% of CPS or above did not exhibit Tm. The PPS/PPSS copolymer obtained with comonomer feed ratio of [DBB]/[CPS] = 95/5 mole% under $240^{\circ}C$ showed even higher molecular weight($M_w=10,300g/mole$) than PPS homopolymer made under similar reaction condition, retaining high crystallinity and thermal stability.

• Polymer(Korea)
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• v.30 no.5
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• pp.432-436
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• 2006

The new dinuclear CGC (constrained geometry complexes) with indenyl and methyl sub-stituted indenyl and polymethylene bridge have been synthesized, and the copolymerization of ethylene and styrene has been studied in the presence of methylalumionoxane. The activity of 12-methylene and 9-methylene bridged dinuclear CGC were 4 times higher than that of 6-methylene bridged dinucleay CGC. This result might be understood by the implication that the steric effect rather than the electronic effect nay play a major role to direct the polymerization behavior of the dinuclear CGC. The dinuclear CGCs are very efficient to incorporate styrene in backbone. The styrene contents in the formed co-polymers ranged from 6 to 45 mol% according to the polymerization conditions. The melting temperature of copolymers disappeared at high content of styrene (about 11 mol%) There is no styrene-styrene diblock sequence in copolymers. This result Indicates that the dinuclear CGC are very effective to generate random copolymer of ethylene and styrene.

• Polymer(Korea)
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• v.30 no.1
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• pp.28-34
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• 2006

A series of methoxypoly(ethylene glycol) $(MPEG)-poly(\varepsilon-co-L-lactide)$ (PCLA) diblock copolymers were synthesized by ring-opening polymerization of a mixture of $\varepsilon-caprolactone$ and L-lactide with different ratios in the presence of $Sn(Oct)_2$. The characterization of MPEG-PCLA diblock copolymers were examined by $^1H-NMR$, GPC, DSC, and XRD. Kinetic study on ring-opening polymerization of monomer mixtures was carried out in various conditions such as a variation with polymerization time, amount of catalyst, and temperature. The highest conversion obtained in 1.2 ratic of initiator venn catalyst at $110\;^{\circ}C$. The biodegradable characterization of MPEG-PCLA diblock copolymers in aqueous solution was carried out by using GPC for $1\~14$ weeks. The biodegradability of MPEG-PCLA diblock copolymers increased as the L-lactide content of diblock copolymers increased. In conclusion, we confirmed the dependence of polymerization rate according to various conditions. In addition, we can control the biodegradability of MPEC-PCLA diblock copolymers by changing the ratio of PCL and PLA block segment.

• Polymer(Korea)
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• v.30 no.6
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• pp.464-470
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• 2006

Diblock copolymers consisting of methoxy Poly (ethylene glycol) (MPEG) and poly (${\epsilon}-ca$ prolactone) (PCL), poly(${\delta}-valerolactone$) (PVL), poly(L-lactide) (PLLA), or poly(L-lactide-co-glycolide) (PLGA) were prepared to compare the characterization of diblock copolymers as a drug carrier. MPEG-PCL, MPEG-PVL, MPEG-PLLA, and MPEG-PLGA diblock copolymers were synthesized by the ring-opening polymerization of ${\epsilon}$-caprolactone or ${\delta}$-valerolactone in the presence of $HCl{\cdot}Et_2O$ as a monomer activator at room temperature and by the ring-opening polymerization of L-lactide or a mixture of L-lactide and glycolide in the presence of stannous octoate at $130^{\circ}C$, respectively. The synthesized diblock copolymers were characterized with $^1H-NMR$, GPC, DSC, and XRD. The micellar characterization of MPEG-polyester diblock copolymers in an aqueous phase was carried out by using NMR, dynamic light scattering, AFM, and fluorescence techniques. Most micelles exhibited a spherical shape in AFM. Thus, ore confirmed that the micelles formed with MPEG-polyester diblock copolymers have possibility as a potential hydrophobic drug delivery vehicle because a hydrophobic drug could be preferentially distributed in the micelle core.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.770-775
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• 1993

Chemical structure of poly(ethylene terephthalate-co-1, 4-cyclohexylene dimethylene terephthalate), P(ET-CT) copolyesters was investigated by High Resolution NMR analysis. The copolymer composition and isomeric ratio were determined by methylene resonance peaks which were separated into three peaks corresponding to ET, trans CT and cis CT units, respectively. The copolymer sequence distribution was evaluated from the carbon resonance peaks connected to carbonyl groups in benzene, indicating died distribution. According to statistics model, these copolyesters are almost random copolymers. The copolymer sequence distribution could be simulated and its averaged length was calculated by random copolymer statistics.