• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.542-543
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• 1993

• Polymer(Korea)
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• v.27 no.1
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• pp.26-32
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• 2003

Poly(vinyl pivalate)(PVPi) telomer containing bifunctional end groups was synthesized through radical telomerization of vinyl pivalate. The number-average molecular weight ($\bar{M}$n) of the synthesized telomers was investigated by GPC, $^1$H-NMR, and viscometric methods. PVPi telomers having a number-average molecular weight ($\bar{M}$n) of 2400~1300 g/mol were obtained. In order to control the molecular weight of telomers, chain transfer constants ($C_s$) of telogen ($CCl_4$) were determined by using the Mayo equation and simulation, which were 1.15, 1.16, and 1.18 at 40, 50, and 6$0^{\circ}C$, respectively. $\bar{M}$n of the synthesized telomers at 6$0^{\circ}C$ were between 5100 and 5400 g/mol at conversion of increasing from 18 to 72%. Those are corresponding to simulation results.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.80-85
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• 1980

The free radical copolymeriaztion of N-vinylurea(VU) with vinyl acetate (VAc) was carried out at $60^{\circ}C$ in three solvents. VU-vinyl alcohol(VA) copolymers were prepared by the methanolysis of the VU-VAc copolymers. From the nitrogen content measurements of VU-VA copolymers, the monomer reactivity ratios for the VU-VAc copolymerization and the values of Alfrey-Price's Q and e for VU were determined. These Q and $\varrho$ values obtained in the cases of using methanol and methanol-dioxane as the polymerization solvents are comparable with those found for other monomers which have > NCO-pendent groups. The $\varrho$ value indicates that the urea group of VU is a electron-donating group. The copolymerization parameter of VU shows a strong effect of the solvents. These results are interpreted to be that VU is in equilibrium with its tautomer at the polymerization temperature.

• Journal of the Korean Chemical Society
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• v.26 no.6
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• pp.421-426
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• 1982

Free radical-initiated copolymerization of diethyl isopropenyl phosphate (DEIPA) with vinyl acetate (VAc) and acrylonitrile (AN) was studied. The monomer reactivity ratios for the monomer pairs, determined at $60^{\cric}C$ using benzoyl peroxide as an initiator, are: ${\gamma}_1$(VAc) = 1.56, ${\gamma}_2$(DEIPA) = 0.44: ${\gamma}_1$(AN) = 15.2, ${\gamma}_2$(DEIPA) = 0.031. The values of the Alfrey-Price constants, Q and e, for DEIPA were calculated to be 0.015 and 0.39, respectively, from the VAc system, and 0.014 and 0.34, respectively, from AN/DEIPA pair. These results indicate that ${\alpha}$-methyl substituent of vinyl phosphate monomer decreases the general reactivity in free radical copolymerization. The intrinsic viscosity and number-average molecular weight of copolymers decreased as their content of DEIPA units increased, indicating a high degree of chain transfer caused by DEIPA, as previously learned in DEVPA system.

• Membrane Journal
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• v.31 no.4
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• pp.268-274
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• 2021

One of the chronic problems in the issue of global warming is the emission of greenhouse gases. Carbon dioxide (CO₂), which accounts for the highest proportion of various greenhouse gases, has been continuously researched by humans to separate it. From this point of view, a poly(vinyl alcohol) (PVA)-based copolymer with acrylic acid monomer was utilized in a gas separation membrane in this study. We employed a free radical polymerization to fabricate PVA-g-PAA (VAA) graft copolymer. It was utilized in the form of a composite membrane on a polysulfone substrate. The proper amount of acrylic acid reduced the crystallinity of PVA and increased CO₂ solubility in separation membranes. In this perspective, we suggest the novel approach in CO₂ separation membrane area by grafting and solution-diffusion.

• Korean Membrane Journal
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• v.11 no.1
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• pp.1-7
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• 2009

This work reports the preparation of proton conductive crosslinked polymer electrolyte membranes by blending poly(vinyl chloride)-g-poly(hydroxyl ethyl acrylate) (PVC-g-PHEA) and poly(vinyl alcohol) (PVA). The PHEA chains of the graft copolymer were crosslinked with PVA using sulfosuccinic acid (SA) via the esterification reaction between -OH of polymer matrix and -COOH of SA. The PVC-g-PHEA graft copolymer was synthesized via atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC backbones. Ion exchange capacity (IEC) continuously increased with increasing concentrations of SA, due to the increasing portion of charged groups in the membrane. However, the water uptake increased up to 20.0 wt% of SA concentration above which it decreased monotonically. The membrane exhibited a maximum proton conductivity of 0.026 S/cm at 20.0 wt% of SA concentration, which is presumably due to competitive effect between the increase of ionic sites and the crosslinking reaction.

• Bulletin of the Korean Chemical Society
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• v.20 no.10
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• pp.1177-1180
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• 1999

The ab initio SCF MO and density functional theory (DFT) studies are carried out on the electrophilic (1a) and electron transfer (1b) addition reactions to the vinyl double bond of aryl vinyl sulfides and ethers. In the electrophilic addition processes, a double bond shift from C3 = C4 to X = C3 occurs with occupation number (1.97) close to the normal two. Due to this shift direct conjugation between the cationic center, X = S or O, and the para electron-donor substituent becomes impossible so that the reaction energies (or log K) are correlated with σ rather than σ+. By contrast, radical cation formation leads to delocalization of the SOMO, a lone-pair πorbital on X, with four major resonance structures in which cationic charge as well as spin density is delocalized over C4 , X and C7 atoms. As a result, partial πbonds are formed over C1 -X and C3 - C4 with occupation numbers (0.82) lower than one. In two of the cannonical structures, III(Ⅹ) and III(X+), direct conjugation between the cationic center, X, and the para substituent is achieved so that a better correlation with σ+ rather than σis obtained. The SCF MO energies at the HF/3-21G* and HF/6-31G* levels lead to very much inferior Hammett correlations in the σ/ σ+ diagnostic criterion. In contrast, the ρvalues evaluated with the DFT energies can give reliable diagnostic distinction between the two addition mechanisms.

• 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.

• Macromolecular Research
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• v.11 no.4
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• pp.273-282
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• 2003

A hydrophilic macromolecular network containing hydrophobic moieties has been prepared by free radical copolymerization of acrylamide and styrene in the presence of poly(vinyl alcohol) (PVA) and its potential as controlled drug delivery carrier was evaluated with tetracycline as a model antibiotic drug. The amount of drug was assayed spectrophotometrically. The network was characterized by optical microscopy, infra-red spectroscopy and structural parameters such as average molecular weight between cross1inks ($M_c$), cross1ink density (q) and number of elastically effective chains ($V_e$) were evaluated. It was found that with increasing concentration of PVA, ST and MBA in the hydrogel, the release rate initially increases but after definite concentrations of the above components the release rate falls. In the case of AM, release rate constantly decreases with increasing AM concentration in the hydrogel.

• Proceedings of the Korean Fiber Society Conference
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• 2001.10a
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• pp.101-102
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• 2001

The control of the stereochemistry during the radical polymerization of vinyl monomer has been a long standing concern and is still one of the most important topic in synthetic polymer chemistry.[1-5] The stereoregularity of vinyl polymers often has significant effect on the properties of polymer materials. Therefore, it is important to devise methods to control stereoregularity during the polymerization reactions. (omitted)