• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.96-101
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• 1987

2-Ethoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyran (1_a$), 2-n-butoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyr an (1b), 2-isobutoxy-6-methoxy-5-cyano-3,4-dihydro-2H-py ran ($1_c$), and 2-ethoxy-6-methoxy-3-methyl-5-cyano-3,4-dihydro -2H-pyran ($1_d$) were prepared by (4 + 2) cycloaddition reaction of methyl $\alpha$-cyanoacrylate with the corresponding alkyl vinyl ethers. Compounds $1_{a-d}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, head-to-tail (H-T) copolymer $3_a$ was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $1_H% NMR and IR spectra, but in the $^{13}C$ NMR spectra significant differences were observed between the H-H and H-T copolymers. Glass transition temperature ($T_g$) of H-H copolymer was higher than that of the H-T copolymer, but thermal decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. Compounds $1_a$, $a_b$, and $1_c$, copolymerized well with styrene by cationic catalyst, but compound 1d failed to copolymerize with styrene. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.4 dl/g.

• 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.

• Macromolecular Research
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• v.13 no.5
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• pp.397-402
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• 2005

To explore the potential of shell crosslinked micelle (SCM) as a drug carrier, the drug release behavior of poly($\varepsilon$-caprolactone)-b-poly(acrylic acid) (PCL-b-PAA) SCMs was investigated. PCL-b-PAA was synthesized by ring opening polymerization of $\varepsilon$-caprolactone and atom transfer radical polymerization of tert-butyl acrylate, followed by selective hydrolysis of tert-butyl ester groups to acrylic acid groups. The resulting amphiphilic polymer was used to prepare SCMs by crosslinking of PAA corona via amidation chemistry. The drug release behavior of the SCMs was studied, using pyrene as a model drug, and was compared with that of non-crosslinked micelles, especially below the critical micelle concentration (CMC). When the shell layers were crosslinked, the drug release behavior of the SCMs was successfully modulated at a controlled rate compared with that of the non-crosslinked micelles, which showed a burst release of drug within a short time.

• Polymer(Korea)
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• v.24 no.3
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• pp.306-313
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• 2000

Polycaprolactone (PCL) macromer containing terminal methacrylate group was synthesized by ring-opening polymerization. The number average molecular weight of PCL macromer was 11600 g/mole and polydispersity index was 1.09. The synthesized PCL macromer was copolymerized with styrene by stable free radical polymerization using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), benzoyl peroxide, and well-defined poly(styrene-g-caprolactone)s were synthesized. The synthesized copolymers was characterized by $^1$H-NMR and gel permeation chromatography equipped with multiangle laser light scattering detector. Thermal properties of graft copolymers were investigated by DSC.

• Bulletin of the Korean Chemical Society
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• v.8 no.2
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• pp.102-105
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• 1987

2-Methoxy-6-methyl-3,4-dihydro-2H-pyran ($1_a$), 2-ethoxy-3,6-dimethyl-3,4-dihydro-2H-pyran ($1_b$), and 2-ethoxy-3-methyl-6-ethyl-3,4-dihydro-2H-pyran ($1_c$) were prepared by (4 + 2) cycloaddition reaction from the corresponding vinyl ketones and alkyl vinyl ethers. Compounds $1_{a-c}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, copolymer of head-to-tail (H-T) was also prepared by free radical copolymerization of the mixture of the corresponding monomers. The H-H copolymer exhibited some differences in its $^1H$ NMR and IR spectra. However, significant differences were showed between the H-H and H-T copolymers in the $^{13}C$ NMR spectra. Also noteworthy was that$T_g$ value of H-H copolymer was higher than that of the corresponding H-T structure. Decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. All the H-H and H-T copolymers were soluble in common solvents.

• Proceedings of the Korean Fiber Society Conference
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• 2002.04a
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• pp.352-354
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• 2002

A series of ABA type triblock copolymers of trimethylene carbonate (TMC) and $\varepsilon$-caprolactone($\varepsilon$-CL) with different molar ratio were synthesized using ethylene glycol as initiator and stannous octoate as catalyst by ring-opening bulk polymerization. The characterization of the triblock copolymers was characterized by $^1$H-NMR, $\^$13/C-NMR, FT-IR, GPC and DSC, and compared with random copolymer. (omitted)

• Macromolecular Research
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• v.11 no.6
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• pp.511-513
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• 2003

Hydroxyl groups were introduced onto the surface of a silicon wafer by O$_2$ plasma treatment. Poly(l-lactide) (1-PLA) was attached onto the surface-modified silicon wafer by the ring-opening polymerization of l-lactide using the hydroxyl group as an initiator. Lamellar single crystals of 1-PLA were grown directly on the 1-PLA-attached silicon wafer from a 0.025% solution in acetonitrile at 5$^{\circ}C$. A well-separated, lozenge-shaped, monolayered lamellar single crystal was prepared because the 1-PLA-attached silicon wafer acts as an initial nucleus.

• Macromolecular Research
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• v.9 no.2
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• pp.100-106
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• 2001

Several star-polymers with aliphatic cores were synthesized by ring opening polymerization (ROP) of $\xi$-caprolactone using stannous 2-ethyl-hexanoate as a catalyst. The star-polymers were thoroughly analyzed by MALDI-TOF mass spectrometry, temperature gradient interaction chromatography and $\^$13/C-NMR to obtain detailed information of the molecular structure. The imperfection of the star-polymers seemed to be originated from restricted participation of sterically hindered hydroxyl groups of initiator. The synthesized star-polymers had narrow molecular weight distributions. Various reaction conditions to control the imperfection were studied.

• Macromolecular Research
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• v.10 no.2
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• pp.54-59
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• 2002

ABA triblock copolymers of L-lactide and trimethylene carbonate with several different compositions were prepared by sequential ring-opening polymerization in the presence of diethylene glycol. Also chain-extension reactions of the resulting copolymers were carried out using hexamethylene diisocyanate to produce relatively high molecular weight polymers, which could be cast into elastomeric tough films. The polymers with certain L-lactide contents were partially crystalline, exhibiting two-phase morphology. The polymer films showed reversible elastic behavior under tensile tension, providing a novel thermoplastic elastomer possessing desirable properties such as biodegradability and good mechanical properties.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.303-303
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• 2006

In-situ ring opening polymerization of ${\varepsilon}-caprolactum$ was carried out in the presence of aminoethylaminopropylisobutyl POSS and stoichiometric amount of adipic acid. The covalent bond formation of POSS on the polyamide was confirmed by the appearance of FT-IR peak at $1123\;cm^{-1}$ that corresponds to the Si-O stretching of POSS structures. Gradual decrease in melting endotherm peak was observed on loading POSS in PA6/POSS nanocomposites. Sharp increase in intrinsic viscosity was observed upto 2.5 wt % loading POSS in the polyamide 6 nanocomposites. These nanocomposites were further characterized using nuclear magnetic resonance, melt viscosity and X-ray diffraction.