• Macromolecular Research
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• v.14 no.4
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• pp.466-472
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• 2006

The kinetic behavior of emulsion polymerizations of styrene in the presence of sulfonated N-hydroxy ethyl aniline (SHEA) was investigated with two initiators: 2,2'-azobisisobutyronitrile (AIBN) and potassium persulfate (KPS). SHEA was synthesized using a stepwise polyurethane reaction method from 3-hydroxy-1-propane sulfonic acid sodium salt, isophorone diisocyanate (IPDI), and N-(2-hydroxyethyl) aniline. Stable core-shell poly(styrene/sulfonated N-hydroxy ethyl aniline, St/SHEA) latex particles were successfully prepared by using an appropriate amount of AIBN, in which SHEA plays the role of 'surfmer', i.e., acting as both a surfactant in the emulsion polymerization and a monomer in the chemical oxidative polymerization. The kinetic behavior was dissimilar to that of typical emulsion polymerization systems. A long inhibition period and low rate of polymerization were observed due to radical loss by the oxidative polymerization of SHEA. It was concluded, due to the low water-solubility of AIBN and retardation reaction by SHEA, that the initial loci of polymerization were monomer droplets. However, growing polymer particles as polymerization loci became predominant as polymerization proceeded. It was suggested that AIBN was more effective than KPS in the preparation of the core-shell type poly(St/SHEA) latex particles. With KPS, no substantial polymerization was observed in any of the samples.

• Fibers and Polymers
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• v.5 no.1
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• pp.75-81
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• 2004

To obtain high molecular weight (HMW) poly(methyl methacrylate) (PMMA) with high conversion, methyl methacrylate (MMA) was polymerized in suspension using a room temperature initiator, 2,2'-azobis(2,4-dimethylvaleronitrile) (ADMVN), and the effects of polymerization conditions on the polymerization behavior of MMA and the molecular parameters of PMMA were investigated. On the whole, the experimental results well corresponded to the theoretically predicted tendencies. These effects could be explained by a kinetic order of ADMVN concentration calculated by an initial rate method and an activation energy difference of polymerization obtained from the Arrhenius plot. Suspension polymerization at 25℃ by adopting ADMVN proved to be successful in obtaining PMMA of HMW (number-average degree of polymerization (P/sub n/): 30,900-36,100) and of high yield (ultimate conversion of MMA into PMMA: 83-93 %) with diminishing heat generated during polymerization. The P/sub n/ and lightness were higher and polydispersity index was lower with PMMA polymerized at lower temperatures.

• Macromolecular Research
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• v.11 no.3
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• pp.146-151
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• 2003

The dependence of electrical conductivity on concentrations of diallyldimethylammonium chloride (DADMAC) monomer, linear poly(DADMAC) and their mixture monomer/poly(DADMAC) in dilute aqueous solution exhibits a linear relationship. It was possible to calculate conversion of DADMAC polymerization by measuring its electric conductivity. Although the electrical conductivity of the poly(DADMAC) solution decreased with increasing its molecular weight, in the process of UV or ionizing radiation polymerization the molecular weight of the polymers could be kept constant in the case of fixed temperature, UV-luminous intensity or dose rate. Based on the method mentioned above, the kinetics of UV induced polymerization of DADMAC in aqueous solution was studied; the overall activation energy of polymerization of DADMAC in the water phase was calculated to be 18.8 kJ mol$^{-1}$ . ${\gamma}$-Radiation-induced polymerization of DADMAC in aqueous solution as a function of absorbed dose was studied as well. The conversion of DADMAC increased quickly with dose before 30 kGy and then increased slowly. The experimental data of both UV- and ${\gamma}$-induced polymerization were verified to be reliable by inverted ultracentrifugation method.

• Polymer(Korea)
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• v.24 no.5
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• pp.610-620
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• 2000

Vinyl acetate (VAc) was polymerized at 30, 40, and 5$0^{\circ}C$ using 2,2'-azobis (2,4-dimethylvaleronitrile) (ADMVN) and tertiary butyl alcohol (TBA) as the initiator and the solvent, respectively. High molecular weight (HMW) atactic poly(vinyl alcohol) (PVA) was prepared by saponifying the poly(vinyl acetate) (PVAc) synthesized. The effect of polymerization conditions were investigated in terms of conversion, degree of branching for acetyl group of PVAc, and molecular weight of both PVAc and PVA. The polymerization rate of VAc in TBA was proportional to the 0.49th power of ADMVN concentration in good accordance with the theoretical value of 0.5. HMW-PVA with high yield could be obtained successfully, probably due to lower polymerization temperature and decreased chain transfer reaction rate which was achieved by adopting ADMVN and TBA. PYAc having average degree of polymerization (P$_{n}$) of 10000~13000 was obtained at the conversion of 35~70%. Saponification of so prepared PVAc yielded PVA having P$_{n}$ of 2400~6100. The syndiotactic diad content increased with decreasing polymerization temperature and increasing VAc concentration due to a steric hindrance effect of TBA during polymerization.

• Journal of Adhesion and Interface
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• v.2 no.2
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• pp.11-19
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• 2001

The phase-transfer catalyzed radical polymerization of styrene was carried out using tricaprylylmethylammonium chloride as a phase-transfer catalyst in a two-phase system of an aqueous $Na_2S_2O_8$ solution and toluene at $60^{\circ}C$ under nitrogen atmosphere. The initial rate of radical polymerization was expressed as the combined terms of concentrations of quaternary onium cation and peroxydisulfate anion in the aqueous phase rather than the fed concentrations of catalyst and $Na_2S_2O_8$. The observed initial rate of radical polymerization was used to analyze the radical polymerization mechanism with a cycle phase-transfer initiation step in the heterogeneous liquid-liquid system. The viscosity average molecular weight of polystyrene was inversely proportional to concentration of $Na_2S_2O_8$ expressed as $[Q^+]([S_2O{_8}^{2-}]{\alpha}_2)^{1/2}$ derived by the radical polymerization mechanism.

• The Transactions of the Korean Institute of Electrical Engineers
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• v.43 no.5
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• pp.802-808
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• 1994

The purpose of this paper is to describe an application of plasma polymerized thin film as an electron beam resist. Plasma polymerized thin film was prepared using an interelectrode capacitively coupled gas-flow-type reactor, and chosen methylmethacrylate(MMA)and methylmethacrylate-tetrameth-yltin(MMA-TMT) as a monomer. This thin films were also delineated by the electron-beam apparatus with an acceleration voltage of 30kV and an expose dose ranging from 20 to 900$\mu$C/cmS02T. The delineated pattern in the resist was developed with the same reactor which is used for polymerization using an argon as etching gas. The growth rate and etching rate of the thin film is increased with increasing of discharge power. Thin films by plasma polymerization show polymerization rate of 30~45($\pm$3) A/min, and etching rate of 440($\pm$30) A/min during Ar plasma etching at discharge power of 100W. In apparently lower than that of conventional PMMA, but the plasma-etching rate of PP(MMA-TMT) was higher than that of PPMMA.

• Restorative Dentistry and Endodontics
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• v.33 no.4
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• pp.341-351
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• 2008

This study investigated the effect of intermittent polymerization on the rate of polymerization shrinkage and cuspal deflection in composite resins. The linear polymerization shrinkage of each composite was measured using the custom-made linometer along with the light shutter specially devised to block the light at the previously determined interval. Samples were divided into 4 groups by light curing method; Group 1) continuous light (60s with light on); Group 2) intermittent light (cycles of 3s with 2s light on & 1s with light off for 90s): Group 3) intermittent light (cycles of 2s with 1s light on & 1s with light off for 120s); Group 4) intermittent light (cycles of 3s with 1s light on & 2s with light off for 180s). The amount of linear polymerization shrinkage was measured and its maximum rate (Rmax) and peak time (PT) in the first 15 seconds were calculated. For the measurement of cuspal deflection of teeth, MOD cavities were prepared in 10 extracted maxillary premolars. Reduction in the intercuspal distance was measured by the custom-made cuspal deflection measuring machine. ANOVA analysis was used for the comparison of the light curing groups and t-test was used to determine significant difference between the composite resins. Pyramid showed the greater amount of polymerization shrinkage than Heliomolar (p < 0.05). There was no significant difference in the linear polymerization shrinkage among the groups. The Rmax was group 4 < 3, 2 < 1 in Heliomolar and group 3 < 4 < 2, 1 in Pyramid (p < 0.05). Pyramid demonstrated greater cuspal deflection than Heliomolar. The cuspal deflection in Heliomolar was group 4 < 3 < 2, 1 and group 4, 3 < 2, 1 in Pyramid (p < 0.05). It was concluded that the reduced rate of polymerization shrinkage by intermittent polymerization can help to decrease the cuspal deflection.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10a
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• pp.1-2
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• 2003

Some new synthetic routes for the preparation of poly (isobutyl vinyl ether) (P(IBVE)) having a controllable molar mass with narrow distribution via catalytic or photoinduced living cationic polymerization and their conversion to corresponding PVA have been developed. It was found that the combination of iodomethyl methyl ether (IMME)-zinc iodide is effective in the initiation of the catalytic and the various combinations of diphenyliodonium halides, well known photocationic initiators (DPIX) with zinc halides (ZnX$_2$) are also useful in photoinduced living cationic polymerization of isobutyl vinyl ether (IBVE). Polymerization both in the catalytic and photoinduced systems precede until the full consumption of the monomer and the rate of polymerization increases as the concentration of the catalyst or photoinitiator. The number average molar mass of the resulting polymer is proportional with % conversion, which is determined by the ratio of monomer consumed and the initial values of the catalyst or initiator. The living nature was also confirmed by subsequent monomer addition technique.

• Applied Chemistry for Engineering
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• v.2 no.3
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• pp.199-208
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• 1991

Carbocationic polymerization is widely applied to prepare polymers from electron-rich monomers. The reaction is usually uncontrollable due to many side reactions and explosively fast rate of polymerization. In a living polymerization, however, the reaction is controlled as designed, and many workers reported many successful cases recently. In this review several ways of living carbocationic polymerization were illustrated, and they were connected together under a basic principle.

• Fibers and Polymers
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• v.2 no.1
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• pp.131-134
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• 2001

Living cationic polymerization behaviors of isobutyl vinyl ehters (IBVE), initiated by iodomethyl methyl ether (IMME)/zinc iodide ($Znl_2$) have been investigated. The polymerization was carried out at 0, -15, and $-30^{\circ}C$ in toluene. It was found that the rate of polymerization increased as the IMME concentration increased and decreased as temperature decreased. 100% conversion was always achieved without exception. Furthermore, the number-average molecular weight ($M_{n}$) of polymers increased in direct proportion to monomer conversion. The molecular weights of polymers were in good agreement with the theoretical values, calculated on the basis that one polymer chain was formed by one IMME molecule and the values of polydispersity index are always less than 1.2, revealing the living nature. The living nature was also confirmed by synthesis of poly(IBVE-b-TBVE) by subsequent monomer addition of t-butyl vinyl ether (TBVE).