• Macromolecular Research
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• v.11 no.5
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• pp.311-316
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• 2003

The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

• Macromolecular Research
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• v.14 no.3
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• pp.338-342
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• 2006

The kinetic features of polymerization with an active site comprising cobalt dihalides ($CoX_2$, where X=Cl, Br, I) activated by methylaluminoxane (MAO) were investigated in 1,3-butadiene polymerization. The catalytic system exhibited the characteristic features of living polymerization. The initiation ($k_i$) and propagation ($k_p$) rate coefficients were estimated using the kinetic model for slow initiation previously reported by Shiono et al. The energy of activation fur the propagation reaction was calculated to be 27-30 $kJmol^{-1}$. The marked changes in reaction rate observed with different halides could be adequately described in terms of variations in the initiation process, with the same Arrhenius curve fitting propagation rate coeffcients estimated from all three halides, suggesting that the halide does not participate in the growing chain end.

• Journal of the Korean Chemical Society
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• v.62 no.3
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• 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.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.323-323
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• 2006

Multi-vinyl monomer, which contains many vinyl groups in a molecule, was prepared by esterification of hydroxyl groups of poly(2-hydroxyethyl methacrylate) with methacryloyl chloride. Then, copper-mediated atom transfer radical polymerization was carried out as a template polymerization. The propagation of polymerization was investigated by kinetic analysis.

• Macromolecular Research
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• v.15 no.1
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• pp.31-38
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• 2007

Pentamethylcyclopentadienyltitanium trichloride, bis(cyclopentadienyl)titanium dichloride ($Cp_2TiCl_2$), and bis(pentamethylcyclopentadienyl)titanium dichloride were used in the polymerization of styrene without the aid of Group I-III cocatalysts. The properties of the resulting polymer indicated that polymerization was more controlled than in thermal polymerization. The kinetic studies indicated that a lower level of termination is present and that the polymer chain can be extended by adding an additional monomer. To elucidate the mechanism of polymerization, a series of experiments was performed. All results supported the involvement of a radical mechanism in the polymerization using $Cp_2TiCl_2$. The possibility of atom transfer radical polymerization (ATRP) mechanism was investigated by isolating the intermediate species. We could confirm the activation step from the reaction of 1-PEC1 with $Cp_2TiCl$ by detecting the coupling product of the generated active radicals. However, the reversible deactivation reaction competes with other side reactions, and it detection was difficult with our model system.

• Journal of the Korea Institute of Military Science and Technology
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• v.12 no.2
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• pp.228-235
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• 2009

We synthesized glycidyl azide monomer(GAM) as a monomer for polymerization of glycidy azide polymer(GAP) which is a promising energetic prepolymer for a plastic-bonded explosive. Using quantitative real-tim in-situ infrared(in-situ IR) spectroscopy, kinetic study on the cationic ring opening polymerization of GAM was carried out. The reaction rate was obtained from monitoring the change of ether C-O stretching band($1050cm^{-1}$) in series IR spectra. The reaction was in accordance with the first-order reaction law for each of reaction temperature at 100/1 mole ratio of [GAM]/[$BF_3*etherate$]. In the ring opening polymerization of GAM, with ratio of [GAM]/[$BF_3*etherate$] to equal 100/1 at various temperature, the activation parameters obtained from the evaluation of kinetic data were ${\Delta}H^*$=14.34kcal/mol, ${\Delta}S^*=-12.31cal/mol{\cdot}K$ and $E_a$=14.89kcal/mol.

• Journal of the Korean Chemical Society
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• v.22 no.6
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• pp.423-430
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• 1978

The initiation mechanism of trioxane polymerization catalyzed by Ti$Cl_4$ in nitrobenzene was investigated. The kinetic studies revealed that the rate of polymerization was drastically decreased by the addition of a minute amount of water or methanol. A third substance as cocatalyst was not required for the polymerization. Measurements of dielectric constants gave no evidence for the zwitterionic mechanism of the polymerization. The electric conductivity measurements of polymerization system and the initiator solution showed that the initiation was started by Ti$Cl_3^+$ cation, formed by a disproportionation of the initiator in nitrobenzene.

• 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.

• Journal of Korean Ophthalmic Optics Society
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• v.8 no.2
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• pp.129-134
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• 2003

A wide variety of unsaturated vinyl derivatives can be induced to undergo free-radical chain polymerization. The capability to carry out a thermodynamically feasible polymerization relies on its kinetic feasibility on whether the proceeds at a reasonable rate under a given set of reaction conditions. Initiator or promoter is often required to achieve the kinetic feasibility. Only a few unsaturated monomers including methyl methacrylate(MMA) are known to absorb light between 250 and 500 nm which is the most convenient wavelength range. Also, the polysilanes with unusual optical and electronic properties have been used as ceramic precursors, deep UV photoresists, photoconductors. The hydrosilation has been used to make many interesting types of silicon containing polymers such as copolymer, dendrimers. Bulk polymerization of monomers with different molar radio of hydrosilanes(9:1 through 1:9) were performed. A quartz test tube charged with monomer and hydrosilane was degassed and irradiated with 250 nm UV for 6 hours. The polymer was taken in toluene, precipitated in hexane, filtered off, and dried. It was found that the initiators appeared to competitively and concurrently function as both chain initiation and transfer agents in the polymerization of vinyl monomers.