• Journal of the Korean Chemical Society
• /
• v.26 no.3
• /
• pp.179-187
• /
• 1982

The copolymerization of N-acryloylpyrrolidone and acrylonitrile was performed in N,N'-dimethylformamide at 50$^{\circ}$C and monomer reactivity ratio was obtained by using IR working curve and Fineman and Ross equation. ($r_1$ = 0.43, $r_2$ = 1.56) It is found that resulting copolymer is good polymeric initiator for anionic graft copolymerization of 2-pyrrolidone. Graft copolymers with polybutylamide (nylon-4) grafts onto poly(NAP-Co-AN) backbone were synthesized and the various effects on the graft copolymerization of 2-pyrrolidone were examined. The rate constants ($K_p$) of graft anionic polymerization at 40 and 50$^{\circ}$C were 2.82${\times}$10 and 2.93${\times}$10(l/mole, min), respectively.

• Elastomers and Composites
• /
• v.48 no.4
• /
• pp.294-299
• /
• 2013

Solution polymerization was conducted with water-soluble methacrylic acid (MAA) as a monomer and potassium persulfate (KPS) as an initiator at a selected temperature between $70^{\circ}C$ and $90^{\circ}C$. When the ratio between MAA and water was reduced or initiator concentration increased, molecular weights decreased. Molecular weights of poly(methacrylic acid) (PMAA) showed nearly no dependence on reaction temperature. The Weissenberg effect was observed in most polymerization reactions, while its effect weakened at $90^{\circ}C$. The polydispersity index was less than 1.5 in most of the reactions. An increase in the stirring speed produced PMAAs with increasing molecular weights. When the stirring speed reached 800 rpm, we retrieved a monodisperse PMAA with both the number and weight average molecular weights of 791,000 g/mol. The glass transition temperature was found to be $162^{\circ}C$.

• Elastomers and Composites
• /
• v.49 no.3
• /
• pp.232-238
• /
• 2014

Solution polymerization was conducted with water-soluble acrylic acid (AA) as a monomer and potassium persulfate (KPS) as an initiator at a selected temperature between $60^{\circ}C$ and $90^{\circ}C$ with water as a reaction medium. When the ratio between AA and water was reduced or initiator concentration increased, molecular weights decreased. An increase in the reaction temperature produced lower molecular weights. The polydispersity index was close to 1.5 in most of the reactions. An increase in the stirring speed up to 400 rpm led to a progressive increase in molecular weights. When the stirring speed reached 800 rpm, however, we found that both the number and weight average molecular weights decreased. The glass transition temperature was nearly independent of moelcular weights and determined to be between $113^{\circ}C$ and $116^{\circ}C$.

• Journal of the Korean Chemical Society
• /
• v.26 no.4
• /
• pp.235-246
• /
• 1982

The free radical polymerization and copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid were investigated. From the result of kinetic investigation of N-acetyl ${\alpha}$-aminoacrylic acid in DMF at $60^{\circ}C$, a rate equation of $R_p$ = $k_p[M]^{0.97}[I]^{0.59}$ was obtained. The overall activation energy for the polymerization was found to be 25.2 kcal/mole. Copolymerization of N-acetyl ${\alpha}$-aminoacrylic acid with acrylic acid and styrene was carried out for the determination of monomer reactivity ratios. The monomer reactivity ratios for the monomer pairs determined at 70.0{\pm}0.1^{\circ}C$ using benzoyl peroxide as an initiator are; $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.49, $r_2$(acrylic acid) = 1.41, $r_1$(N-acetyl ${\alpha}$-aminoacrylic acid) = 0.44, $r_2$(styrene) = 0.91. The values of Alfrey-Price's Q and e parameters for N-acetyl ${\alpha}$-aminoacrylic acid were calculated to be 0.51 and 0.16 for the both systems. Differential thermal analysis and thermogravimetry showed that acrylic acid copolymers have poorer thermal stability as compared with the homopolymer of N-acetyl ${\alpha}$-aminoacrylic acid.

• Polymer(Korea)
• /
• v.24 no.4
• /
• pp.437-444
• /
• 2000

Propylene polymerizations were carried out by using rac-Et(Ind)$_2$ZrCl$_2$ (Zirconocene catalyst) and a commercial third generation Ziegler-Natta catalyst in a semibatch reactor. From the polymerization reactions, the optimum reaction conditions and the physical properties of polymers produced from each catalyst system were investigated. The optimum reaction temperatures of rac-Et(Ind)$_2$ZrCl$_2$ and Ziegler-Natta catalyst were 5$0^{\circ}C$, 4$0^{\circ}C$, respectively. On the basis of the results for the produced polymer particle size distributions and the catalytic activities of polymerization reaction, the reaction temperature should be considered as an important factor for the successful polymerization reactions. Especially, the polymer was conglomerated in the higher reaction temperature. It was found that there was an upper limitation to co-catalyst concentration. Reaction rates and polymer yields rather decreased with increasing the concentration of to-catalyst, i.e., MAO and TEAl affected only polymerization activities, but the PEEB in Ziegler-Natta catalyst system affected isotactic indexes of produced polymer as well as activities. Based on these observations, the production yield seems to exhibit a first order lineal relationship to the partial pressure of monomer.

• Polymer(Korea)
• /
• v.24 no.3
• /
• pp.287-298
• /
• 2000

In preparing micron-sized monodisperse polystyrene beads by dispersion polymerization, the conversion, and the particle size and its distribution were affected by the reaction temperature, concentration of the monomer, solvent and initiator, molecular weight and concentration of the steric stabilizer, amount of oxygen existing in the reactor, and an appropriate combination of these starting materials. Ethanol as a dispersing agent, styrene as a monomer, PVP as a steric stabilizer, AIBN as an initiator, DVB as a cross-linking agent and toluene as a co-solvent were the basic materials for the synthesis. The reaction rate and the conversion were increased with the reaction temperature and the amount of DVB from 1 to 4%, and the conversion was saturated after 10 hours of the reaction time. The optimum reaction recipe for the preparation of the monodisperse PS beads was 25% styrene monomer, 0.5% DVB, 25% toluene, 10-15% PVP, and 2 and 4% AIBN, thereby, 3.9~4 ${\mu}{\textrm}{m}$ and 3.4~9.3 ${\mu}{\textrm}{m}$ of polystyrene beads, respectively, were successfully synthesized.

• Polymer(Korea)
• /
• v.28 no.2
• /
• pp.121-127
• /
• 2004

The instantaneous removal of ethylene glycol is very important fur obtaining high molecular weight polymer because of the reversibility of the polycondensation reaction of poly(ethylene naphthalate)(PEN). In this study, we investigated the mass transfer phenomena in the thin film of PEN oligomer where the polycondensation reaction took place at 280$^{\circ}C$ and under 0.1mmHg. In case of less than 0.025cm film thickness the mass transfer resistance through the thin film of the polymer melt was not so high that the overall reaction rate was governed only by the polycondenstion reaction. Both the mass transfer model and the diffusion model predicted the experimenatal data well but the diffusion model showed faster reaction rate in the low molecular weight range than the mass transfer model . It was estimated from the two models that the diffusivity was 4.7${\times}$10$\^$-6/$\textrm{cm}^2$/sec and the mass transfer coefficient was 1.4 ${\times}$10$\^$-4/cm/sec both of which were smaller than In case of poly(ethylene terephthalate).

• Applied Chemistry for Engineering
• /
• v.4 no.2
• /
• pp.300-307
• /
• 1993

The phase-transfer polymerization of methyl methacrylate with tricaprylmethylammonium chloride-$Na_2S_2O_4-CCl_4$ initiator system was investigated in an aqueous-organic two-phase system. The observed rates of polymerization were compared with those obtained from the polymerization mechanism proposed with a cyclic phase-transfer initiation step. The rate of polymerization was found to be proportional to the concentration of $Q^+$ and square root of ${S_2O_4}^{-2}$ in the aqueous solution and the feed quantity of $CCl_4$ and MMA.

• Journal of the Korean Chemical Society
• /
• v.40 no.7
• /
• pp.467-473
• /
• 1996

Although a polypyrrole shows better electrical conductivity, 100∼400 ${\Omega}^{-1}cm^{-1}$, than other organic conducting polymers, its electrical conductivity will be worsen in the presence of the oxygen due to its easy oxidation. On the other hand, polythiophene shows better stability in the air while its electrcal conductivity is poor compared to the polypyrrole. We succeed to develope the mixed polymer electrode that is stable in the air and shows a good redox characteristics. The mixed polymer electrode has been prepared by the electrical polymerization of polypyrrole on the Pt electrode as 1.70 C$cm^{-2}$ and then coating with polythiophene as 0.34 C$cm^{-2}$. The polymerization rate of polythiophene was $3.89{\times}10^{-8}$ at the bare Pt electrode and $6.07{\times}10^{-8}cms^{-1}$ at the mixed polymer electrode. And the standard rate constants of each electrode were $5.16{\times}10^{-6}\;and\;3.94{\times}10^{-4} cms^{-1}$ respectively. Also, the electrocatalytic rate of the polypyrrole polymer electrode was $3.45{\times}10^{-3}cm^3mol^{-1}s^{-1}.$ We found the immobilized layer at the modified electrode acted as an electrocatalyst. Finally, this polymerization process at the Pt electrode was the electron transfer controlled, but that the mixed polymer electrode was the diffusion and charge transfer controlled.

• Applied Chemistry for Engineering
• /
• v.20 no.1
• /
• pp.75-79
• /
• 2009

The ratio of aniline dimer (p-aminodiphenylamine), which is a nucleation site of chain growth in a chemical polymerization of aniline monomer, to aniline monomer was controlled to synthesize polyaniline with the molecular weight ($M_w$) between 10000 and 20000 g/mol. The result of OCP measurement showed that the reaction rate of polymerization was increased as the mole ratio of dimer was increased. The increase in the molar ratio of dimer resulted in the shift of absorption wavelength of polyaniline to the short wavelength region on measurement of UV/Vis and the decrease of molecular weight on the measurement of GPC.