• Macromolecular Research
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• v.17 no.4
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• pp.240-244
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• 2009

High molecular weight(MW), 3-arm star poly(methyl methacrylate)(PMMA) with a narrow MW distribution($M_n$=570,000 g/mol, PDI=1.36) was successfully synthesized by activators regenerated by electron transfer(ARGET) atom transfer radical polymerization(ATRP). The polymerization was carried out with a trifunctional initiator/$CuBr_2$/N,N,N',N",N"-pentamethyldiethy lenetriamine(PMDETA) initiator/catalyst system in the presence of a tin(II) 2-ethylhexanoate [$Sn(EH)_2$] reducing agent at $90^{\circ}C$. The concentration of the copper catalyst was as low as 30 ppm, and a high initiation efficiency of the initiating sites was obtained. The chain-end functionality of the high MW, 3-arm star PMMA was confirmed by a chain extension experiment with styrene via ARGET ATRP, using the same catalyst system.

• Journal of the Korea Institute of Military Science and Technology
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• v.3 no.1
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• pp.164-175
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• 2000

Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

• Korean Journal of Materials Research
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• v.20 no.9
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• pp.472-477
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• 2010

$Al_2O_3$ has received wide attention with established use as a catalyst and growing application in structural or functional ceramic materials. On the other hand, the boehmite (AlO(OH)) obtained by sol-gel process has exhibited a decrease in surface area during phase transformation due to a decline in surface active site at high temperature. In this work, $Al_2O_3$-CuO/ZnO (ACZ) and $Al_2O_3$-CuO/CeO (ACC) composite materials were synthesized with aluminum isopropoxide, copper (II) nitrate hemi (pentahydrate), and cerium (III) nitrate hexahydrate or zinc (II) nitrate hexahydrate. Moreover, the Span 80 as the template block copolymer was added to the ACZ/ACC composition to make nano size particles and to keep increasing the surface area. The ACZ/ACC synthesized powders were characterized by Thermogravimetry-Differential Thermal analysis (TG/DTA), X-ray Diffractometer (XRD), Field-Emmision Scanning Electron Microscope (FE-SEM), Bruner-Emmett-Teller (BET) surface analysis and thermal electrical conductivity (ZEM-2:M8/L). An enhancement of surface area with the addition to Span 80 surfactant was observed in the ACZ powders from 105 $m^2$/g to 142 $m^2$/g, and the ACC powders from 103 $m^2$/g to 140 $m^2$/g, respectively.