• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1269-1276
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• 1999

Metallocenes, whether using a cocatalyst or not, act as catalysts in ethylene polymerization. The positive charge on the transition metal of a metallocene might have an important role in polymerization as an active site in our model approach. Using semiempirical calculations in the absence of cocatalyst, we show one of the possibilities that the positive charge on a metallocene might be more easily transferred through the Cp ring of a ligand to the ethylene than to transfer directly from the transition metal to the ethylene. In these calculations, the charge on titanium in an eight C2H4 system is transferred and a polymer chain is produced. This reaction takes place only when ethylenes are arranged in a particular direction with respect to the ring, but does not take place for ethylenes near Ti or Cl atoms. The same mechanism is shown for a metallocene ligand which is sterically hindered or where the Cp ring is replaced by fluorenyl. These results suggest an entirely new polymerization mechanism in the absence of a cocatalyst in which the Cp ring is the active site.

• Textile Coloration and Finishing
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• v.1 no.1
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• pp.7-18
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• 1989

The distinguishing characteristic of the glow discharge is that chemical reaction induced by partially ionized gases are limited only to the substrate surface. Most studies have been done on the plasma etching and polymerization. The graft polymerization in vapour phase by cold plasma has been rarely investigated. In this study the system of tub3ar reaction chamber with capacitively coupled electrode of alternative current of 60 Hz was employed for the graft polymerization. The graft polymerization of Acylic Acid(AA) onto the poly (ethylene terephthalate) (PET) was carried out by treatment of PET film and fabric by cold plasma (glow discharge of argon gas), followed by the supply of AA vapour. The graft yield was about 1 wt%. The surface property was determined by contact angle, the surface tension was evaluated by zisman’s plot and equation of surface tension mesurement. The results were as follows: 1. In order to obtain lower contact angle, it was effective to avoid the vicinity of electrodes for a setting position of substrate. 2. Contact angle affected on the monomer pressure and its duration of exposure to the acid vapour. 3. Polymer radical formation was influenced by the changes of the value of current density and plasma treatment time. 4. Total surface tension of plasma grafted PET film increased. With an increase in the carboxylic acid content, the dispersion force decreased, while, the polar force and hydrogen bonding force increased. 5. The contact angle decreased from $75^\circ$ to around $30^\circ$ by plasma grafting. There was no ageing effect on the contact angle after 4 months.

• Polymer(Korea)
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• v.37 no.1
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• pp.80-85
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• 2013

Anionic polymerization of hexafluoropropylene oxide (HFPO) was investigated under various reaction conditions such as various hexafluoropropylene (HFP) oligomers composed of dimer and trimer, reaction temperatures, and feeding rates of hexafluoropropylene oxide monomer. HFP oligomer was synthesized from cesium fluoride (CsF) and HFP in tetraethyleneglycol dimethylether (TG). Under 5 g of CsF, 200 g of HFP, 10 g of TG, and reaction temperature $30^{\circ}C$, HFP dimer content in oligomer was relatively increased. HFPO oligomer with a high molecular weight ($M_w$ 3600) was synthesized in conditions of reaction temperature $0^{\circ}C$, HFP oligomer with 35.1% of dimer, and 1.85 g/min of HFPO feeding rate. Otherwise, chain transfer was increased under unoptimized reaction conditions. Consequently, it was found that reaction conditions impact chain propagation and chain transfer in the anionic polymerization of HFPO.

• Analytical Science and Technology
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• v.17 no.3
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• pp.225-229
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• 2004

The effect of the silicon acrylate as a reactive additive on the UV-curing photopolymerization reaction was studied by micro raman technique. For the study, acrylate systems and Darocur 1173 were used as oligomer and monomers, and a photo initiator, respectively. The content of silicon acrylate was within the range of 0-3 wt%. The extent of photo-polymerization reaction as a function of depth from the air interface was obtained from the conversion ratio of acrylate double bond calculated from the intensities of measured bands at $1410cm^{-1}$ and at $1635cm^{-1}$. Micro raman spectroscopic technique can be an useful tool for the investigation of the factors, which can affect the reaction progress, such as oxygen inhibition, composition of the formulations, depth, etc.

• Applied Chemistry for Engineering
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• v.20 no.3
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• pp.322-328
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• 2009

Emulsion polymerization of octamethylcyclotetrasiloxane (OMCTS) was conducted under ultrasonic irradiation. Two sources of ultrasound with different intensities and frequencies of 20 KHz and 40 KHz were used for horn and bath type reactor, respectively. A combined process of horn and bath was also investigated. The effectiveness of the reaction systems was investigated by measuring conversion as well as intrinsic viscosity of the products. The influence of reaction temperature and sonication time on the progress of sonochemical polymerization was examined. It was found that conversion of greater than 80% and high viscosity were achieved within a few minutes of sonication in a horn type reactor, however, conversion and viscosity showed maximum values depending upon the sonication time. In a bath type reactor where a relatively weak intensity was maintained, longer duration time of more than one hour of sonication was required to reach a high level of conversion and viscosity. Compared with the horn type system, the conversion and viscosity in the bath type reactor were increased along with the sonication time. When the polymerization was carried out in a combined system of horn and bath, the evolution of conversion and molecular weight was quite different from the other cases. For the given geometry of reaction system, acoustic analysis using a commercial software was carried out and the results were correlated with experimental observation.

• Korean Chemical Engineering Research
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• v.58 no.4
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• pp.651-657
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• 2020

Fluidization processes in which solid particles vividly move like gas or liquid have been widely used in various industrial sectors, such as thermochemical energy conversion and polymerization processes for general purpose polymer resins. One of the general purpose polymer resins, LLDPE(Linear low-density polyethylene) resins have been produced in bubbling fluidized bed processes in the world. In a bubbling fluidization polymerization reactors, LLDPE particles with relatively larger particle size and low density are fluidized by hydrogen gas for polymerization reaction. Though LLDPE polymerization reactors are one of bubbling fluidization processes, slugs that have negative impact for reaction exist or occur in these processes. Therefore, the fluidization state of LLDPE particles was investigated in a simulation model similar to a pilot-scale polymerization reactor (0.38 m l.D., 4.4 m High). In particular, the effect of gas velocity (0.45-1.2 m/s), solid density (900-199 kg/㎥), solid sphericity (0.5-1.0), and average particle size (120-1230 ㎛), on bed height and fluidization state were measured by using a CPFD(Computational particle-fluid dynamics) method. With CPFD analysis, the occurrence of a flat slug was visualized. Also, the change in particle properties, such as particle density, sphericity, and size, could reduce the occurrence of slug and bed expansion.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.21-26
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• 2005

Experimental researches on the preparation of porous polymeric monoliths in supercritical carbon dioxide have been performed and the effects of monomer and polymerization parameters on the physical properties of the monolith prepared were examined. Polymerizations were carried out in the high pressure stainless steel reactor with sapphire window to show the phase change during the polymerization reaction, and continuous and dry porous monolithic polymer could be obtained. The specific surface area of monolithic polymer increased with monomer contents in reaction mixture and reaction pressure. The Rockwell hardness could be enhanced by the addition of co-monomer MMA in reaction mixtures.

• Applied Chemistry for Engineering
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• v.25 no.5
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• pp.526-530
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• 2014

Polystyrene-poly(etheramic acid) core-shell particles were prepared by dispersion polymerization of styrene using poly(etheramic acid) obtained by the reaction of 2,2'-bis[4-(3,4-dicarboxyphenoxy) phenyl]propane dianhydride and 3,5-diamniobenzoic acid as a stabilizer. 4-Vinylbenzyltrimethylammonium chloride was used as a comonomer to increase the binding efficiency of poly(etheramic acid). When the ethanol-water mixture (7 : 3) was used as a reaction medium, particles were stabilized well and the size distribution of particles was fairly narrow. The particle size increased with the amount of styrene. The particles polymerized in the dimethylformamide-water mixture had a broad size range. Polystyrene-poly(etheramic acid) core-shell particles were transformed to polystyrene-polyetherimide core-shell particles by the chemical imidization of shells.

• Macromolecular Research
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• v.17 no.5
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• pp.346-351
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• 2009

$TiCl(O-i-Pr)_3/SiO_2$ and $Ti(O-i-Pr)_4/SiO_2$ were prepared by immobilizing chlorotitanium (IV) isopropoxide ($TiCl(O-i-Pr)_3$) and titanium (IV) isopropoxide ($Ti(O-i-Pr)_4$), to pretreated silica. The effect of the polymerization reaction conditions on the catalytic activity and characteristics of the resulting PLA were investigated. The catalytic conversion, molecular weight and polydispersity index (PDI) of the PLA produced on the titanium alkoxide supported catalysts increased proportionally with the reaction temperature. When the PLA was synthesized in bulk polymerization, the PLA produced with the supported catalysts had higher molecular weight than those with homogeneous catalysts. The melting temperature of the polymer produced with silica supported alkoxide catalysts was approximately $170-180^{\circ}C$.

• Journal of the Korean Applied Science and Technology
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• v.6 no.1
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• pp.1-7
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• 1989

To developed new process for obtaining maximum molecular weight of anionic acrylamide and acrylic acid copolymer by inverse emulsion polymerization. Concentration of initiator, reducing agent, surfactant and mole ratio of acrylamide-acrylic acid were studied for the process. Semi-batch processes with method of redox, control of reaction temperature, feeding method of monomer and reaction time, was suitable for maximum molecular weight of P(AMAC) from this process obtained $3.09\;{\time}\;10^6({\bar{M}}n.)$ and $4.41\;{\time}\;10^6({\bar{M}}w.)$ in molecular weight measured by the intrinsic viscosity method. inverse emulsion polymerization mechanism of P(AMAC) does not followed the Smith-Ewart and Medvedev theory, but selected for concentration of initiator, reducing agent, surfactant, water solubility of monomer.