• Macromolecular Research
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• v.15 no.1
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• pp.17-21
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• 2007

A series of new, vinyl sulfone-containing monomers was prepared by p-aminophenyl vinyl sulfone (1) with various acid chlorides such as adipoly chloride, terephthaloyl chloride and isophthaloyl chloride. Finally, tertiary amine-containing poly(amide-sulfone)s were prepared by the Michael-type addition polymerization using N,N-dimethylethylenediamine (DMEDA), p-phenylenediamine and piperazin. To evaluate the relevant properties for permselective membranes and enzyme substrate, various physical properties such as molecular weight, solubility, quaternization behavior and thermal properties were examined.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1884-1890
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• 2011

A series of Ni(II) and Pd(II) complexes bearing N4-type tetradentate ligands, [Ni($X^1X^2$-6-$Me_2bpb$) 1] and [Pd($X^1X^2$-6-$Me_2bpb$) 2]; 6-$Me_2bpb$ = N,N'-(o-phenylene)bis(6-methylpyridine-2-carboxamidate), $X^1$ = Cl, H, or $CH_3$, $X^2$ = $NO_2$, Cl, F, H, $CH_3$, or $OCH_3$) were designed, synthesized, and characterized to investigate electronic and steric effects of ligand on the norbornene polymerization catalysts. Using modified methylaluminoxanes as an activator, the complexes exhibited high catalytic activities for the polymerization of norbornene and the nickel complexes exhibited better catalytic activity the palladium complexes. Ni complex 1a with $NO_2$ group on the benzene ring showed the highest catalytic activity of $4.9{\times}10^6$ g of PNBEs/$mol_{Ni}{\cdot}h$ and molecular weight of $15.28{\times}10^5$ g/mol with PDI < 2.30. Complexes with electron-withdrawing groups are more thermally stable (> 100 $^{\circ}C$), and tend to afford higher polymerization productivities than the ones having electron-donating groups. Amorphous polynorbornenes were obtained with good solubility in halogenated aromatic solvents. A vinyl addition mechanism has been proposed for the catalytic polymerization.

• Korean Journal of Materials Research
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• v.30 no.6
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• pp.273-278
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• 2020

This research is conducted to analyze the compatibility of used monomers and produce the high functional hydrogel ophthalmic polymer containing silane and nanoparticles. VTMS (vinyltrimethoxysilane), TAVS [Triacetoxy(vinyl)silane] and cobalt oxide nanoparticles are used as additives for the basic combination of SilM (silicone monomer), MMA (methyl methacrylate) and MA (methyl acrylate). Also, the materials are copolymerized with EGDMA (ethylene glycol dimethacrylate) as cross-linking agent, AIBN (thermal polymerization initiator) as the initiator. It is judged that the lenses of all combinations are optically excellent and thus have good compatibility. Measurement of the optical and physical characteristics of the manufactured hydrophilic ophthalmic polymer are different in each case. Especially for TAVS, the addition of cobalt oxide nanoparticles increases the oxygen permeability. These materials are considered to create synergy, so they can be used in functional hydrogel ophthalmic lenses.

• Bulletin of the Korean Chemical Society
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• v.33 no.12
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• pp.4131-4136
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• 2012

Several palladium complexes containing ${\beta}$-ketoiminate and ${\beta}$-diketiminate ligands successfully produced poly(DCPD) possibly via vinyl addition. It was found that catalysts with ${\beta}$-diketiminate ligands containing bulkier aryl substituents showed the highest activity in the presence of MAO as a cocatalyst. Purity of DCPD is quite essential for the higher activity and small amount of organic solvent such as $CH_2Cl_2$ and toluene is required to reduce the viscosity of the reactant mixture for the higher activity. $^1H$ NMR spectra of produced polymers with N,N-dimethylanilinium tetra(pentafluorophenyl)borate (N,N-DAPFAr"$_4$) show that 5,6-double bond of DCPD is removed with 2,3-double bond remaining. Produced poly(DCPD) with MAO cocatalyst is quite rigid and insoluble in common organic solvents but rather brittle.

• Polymer(Korea)
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• v.27 no.5
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• pp.429-435
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• 2003

Vinyl addition copolymerizations of norbornene (NB) and 5-vinyl-2-norbomene (VNB) were carried out using a cationic η$^3$-allyl palladium catalyst in the various mole ratio of comonomers. The copolymers could be obtained in good yield (65∼85%) with high weight-average molecular weights (M$_{w}$ > 760,000). Depending on increasing VNB contents, the molecular weight and yield of the copolymers decreased. FT-IR analysis confirmed that actual contents of VNB in polymer were proportional to the feeding content of VNB. From $^1$H-NMR spectroscopy, we found that both exo and endo VNB isomer were copolymerized with NB. Thermal stabilities of NB-VNB copolymers were independent on the VNB content and their initial decomposition temperatures were about 300 C. The NB-VNB copolymers were followed by epoxidation by using m-CPBA and hydroxylation by 9-BBN, respectively, and these post-polymers were characterized by FT-IR spectroscopy and $^1$H-NMR analysis..

• Macromolecular Research
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• v.17 no.4
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• pp.250-258
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• 2009

One-step seeded polymerization was used to prepare $7{\sim}10{\mu}m$ of crosslinked monodisperse spheres with four crosslinking agents using $4.68{\mu}m$ poly(methyl methacrylate)(PMMA) seed particles in aqueous-alcoholic media in the absence of the swelling process. The crosslinking agents used were ethylene glycol dimethacrylate(EGDMA), allyl methacrylate(AMA), 1,6-hexanediol diacrylate(HDDA) and trimethylolpropane trimethacrylate(TMPTMA). The effects of the type and concentration of the crosslinking agents on the swelling, pore size, thermal property of the networks and morphology of the particles were studied. The chemical structures and concentrations of the crosslinking agents affected both the swelling ratio and the porosity of the networks. In addition, the chemistry of the reactive vinyl group and chain length of the crosslinking agents affected the stability of the monodisperse particles of the ultimate morphology.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10b
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• pp.177-178
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• 2003

Many researchers have made efforts to control the stereoregularity in radical polymerization of vinyl monomers because the physical and chemical properties of the polymer are significantly affected by the stereostructure.[1]-[4] In general, monomer design, reaction conditions(e.g. solvent, temperature, and monomer concentration), and additives can alter the stereochemistry of the radical polymerization of acrylic monomer. (omitted)

• Polymer(Korea)
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• v.28 no.3
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• pp.245-252
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• 2004

We synthesized the vinyl addition-type polynorbomene copolymers using two monomers [5-hexyl-2-norbornene (HNB) and 5-methyleste-2-norbornene(MES-NB)] by means of a cationic ${\eta}^3$-allyl palladium catalyst system{[(${\eta}^3$-allyl)palladium(tricyclohexylphosphine) trifluoroacetate] and [lithium tetrakis(pentafluorophenyl) borate ${\cdot}$2.5 etherate]}. The molecular weights and yields of copolynorbomenes polymerized in various conditions were measured to investigate an optimum polymerization conditions to obtain highly ester-functionalized polynorbomenes. As a Pd catalyst content increased, the molecular weights (Mw) of polymers decreased while polymer yields increased. Also, as a Li cocatalyst content increased, the Mw’s and yields of polymers increased at the same time. The Mw’s of copolymers were also controlled by chain transfer agents such as 1-hexone, 1-octene and 1-decene, and we found that longer 1-decene and 1-octene were more efficient to reduce the Mw’s of polynorbornenes than 1-hexene. On the other hand, the content of chain transfer agents did not give influence significantly on polymer yields. From the $^1$H-NMR and GPC analysis of HNB/MES-NB(feed ratio of 40/60 mol%) copolymer, we found that this copolymer had an about 25 mol% of ester portion and a high molecular weight of 270,000.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.296-296
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• 2006

Highly temperature stable mesoporous materials have excellent properties and potential applications. Here we show a novel poly(vinyl)silazane-block-polystyrene diblock copolymer, which was synthesized by controlled/living free radical polymerization with reversible addition fragmentation chain transfer (RAFT) route. The obtained diblock copolymer occurs the phaseseparation on the nanoscale to form ordered nanostructure, which is converted to mesoprorous ceramic after heating at 800oC. This route demonstrates the preparation of highly temperature stable mesoporous silicon carbon nitrides (SiCN) ceramic film directed from highly cross-linking poly(vinyl)silazane blocks with high ceramic yield, which is different from previous pathway.

• Applied Chemistry for Engineering
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• v.27 no.3
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• pp.313-318
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• 2016

In this study, an amorphous silica was functionalized with aminosilane, N-[(3-trimethoxysilyl)propyl]ethylenediamine (2NS) and the late transition metal catalysts including ($(DME)NiBr_2$ and $PdCl_2$(COD)) were subsequently immobilized on the functionalized amorphous silica for norbornene polymerization. Effects of the polymerization temperature, polymerization time, Al/Ni molar ratio, and type of co-catalyst on norbornene polymerization were investigated. Unsupported late transition metal catalysts did not show any activities for norbornene polymerization. However, the $SiO_2$/2NS/Ni catayst with MAO system, with increasing polymerization temperature, increased the polymerization activity and decreased the molecular weight of the polynorbornene (PNB). Furthermore, the catalyst when increasing polymerization temperature caused the decrease in both the polymerization activity and molecular weight of PNB. This confirmed that the stability of $SiO_2$/2NS/Ni at a high temperature was greater than that of $SiO_2$/2NS/Pd. Also the longer polymerization time resulted in the higher conversion of norbornene for both catalysts. When the Al : Ni molar ratio was 1000 : 1, the highest activity (15.3 kg-PNB/($({\mu}mol-Ni^*hr$)) but lowest molecular weight ($M_n$ = 124,000 g/mol) of PNB were achieved. Also $SiO_2$/2NS/Ni catalyst with borate/TEAL resulted in diminishing the polymerization activity and molecular weight of PNB with increasing the polymerization temperature.