• Macromolecular Research
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• v.13 no.3
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• pp.229-235
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• 2005

Various alkoxyamine initiators for nitroxide mediated radical polymerization (NMRP) were prepared in high yields by a simple substitution reaction of nitroxide anions with benzyl bromide. The required nitroxide anions were easily generated by treating either nitroxide free radicals or hydroxy amine with an alkali metal such as sodium or potassium in THF. This method is both practical and efficient, since the ionic conditions prevent other side reactions from occurring, such as the self-coupling or oligomerization reactions that are observed in the case of radical trapping conditions. To demonstrate the utility of the resulting alkoxyamine initiators, end- and telechelic-alkoxyamine PEG macroinitiators derived from the alkoxyamines were synthesized by a simple chemical modification, and used for the preparation of PEG-b-PS and PS-b-PEG-b-PS block copolymers by NMRP.

• Polymer Science and Technology
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• v.22 no.4
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• pp.330-338
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• 2011

• Journal of Integrative Natural Science
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• v.2 no.1
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• pp.18-23
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• 2009

This minireview provides the chosen examples of our recent discoveries in the polymerization of hydrosilanes, dihydrosilole, lactones, and vinyl derivatives using various catalysts. Hydrosilanes and lactones copolymerize to give poly(lactone-co-silane)s with $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) catalyst. Hydrosilanes (including dihydrosilole) reduce noble metal complexes (e.g., $AgNO_3$, $Ag_2SO_4$, $HAuCl_4$, $H_2PtCl_6$) to give nanoparticles along with silicon polymers such as polysilanes, polysilole, polysiloxanes (and silicas) depending on the reaction conditions. Interestingly, phenylsilane dehydrocoupled to polyphenylsilane in the inert nitrogen atmosphere while phenylsilane dehydrocoupled to silica in the ambient air atmosphere. $Cp_2M/CX_4$ (M = Fe, Co, Ni; X = Cl, Br, I) combination initiate the polymerization of vinyl monomers. In the photopolymerization of vinyl monomers using $Cp_2M/CCl_4$ (M = Fe, Co, Ni), the photopolymerization of MMA initiated by $Cp_2M/CCl_4$ (M = Fe, Co, Ni) shows while the polymerization yield decreases in the order $Cp_2Fe$ > $Cp_2Ni$ > $Cp_2Co$, the molecular weight decreases in the order $Cp_2Co$ > $Cp_2Ni$ > $Cp_2Fe$. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. The photopolymerizations are not living. Many exciting possibilities remain to be examined and some of them are demonstrated in the body of the minireview.

• Polymer(Korea)
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• v.35 no.5
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• pp.395-401
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• 2011

MWNT/PMMA and MWNT/PDMAEMA nanocomposites were prepared using an atom transfer radical polymerization (ATRP). The FTIR and XRD analysis results showed that the nanocomposites were composed of MWNTs grafted by either PMMA(PMMA-g-MWNTs) or PDMAEMA(PDMAEMA-g-MWNTs). A controlled living radical polymerization of ATRP was characterized by the thermogram analysis for the nanocomposites. The morphologies of prepared nanocomposites were analyzed by transmission electron microscopy. Raman analysis results for the nanocomposites showed that there occurred covalent bonding between acrylic polymers and MWNTs.

• Polymer(Korea)
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• v.34 no.2
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• pp.159-165
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• 2010

Dipyridine-terminated polystyrenes and polybutadienes were synthesized by the chain endfunctionalization reaction of polystyryllithium (PSLi) and polybutadienyllithium (PBDLi) with di(2-pyridyl) ketone(DPK) using a living anionic polymerization method in the Ar-glove box. Living polymeric lithiums with low molecular weights (Mw=1000~2000 g/mol) were used to investigate the chain end-functionalization yield with DPK and the degree of coupling reaction by the attack of organolithium to the pyridine ring in the presence of TMEDA using GPC, $^1H$-NMR, $^{13}C$ analysis. DPK-terminated PBD exhibited much higher functionalization yield and less amount of coupling reaction compared with DPK-terminated PS. 86% functionalization yield with 9% degree of coupling was obtained when the PBDLi was added dropwise to DPK solution at room temperature. The functionalization yield was increased as the reaction temperature decreased, however, no LiCl effect was observed in this chain end-functionalization reaction with DPK.

• Macromolecular Research
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• v.14 no.3
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• pp.287-299
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• 2006

To successively synthesize star-branched polymers, we developed a new iterative methodology which involves only two sets of the reactions in each iterative process: (a) an addition reaction of DPE or DPE-functionalized polymer to a living anionic polymer, and (b) an in-situ reaction of 1-(4-(4-bromobutyl)phenyl)-1-phenylethylene with the generated 1,1-diphenylalkyl anion to introduce one DPE functionality. With this methodology, 3-, 4-, and 5-arm, regular star-branched polystyrenes, as well as 3-arm ABC, 4-arm ABCD, and a new 5-arm ABCDE, asymmetric star-branched polymers, were successively synthesized. The A, B, C, D, and E arm segments were poly(4-trimethylsilylstyrene), poly(4-methoxystyrene), poly(4-methylstyrene), polystyrene, and poly(4-tert-butyldimethylsilyloxystyrene), respectively. All of the resulting star-branched polymers were well-defined in architecture and precisely controlled in chain length, as confirmed by SEC, $^1H$ NMR, VPO, and SLS analyses. Furthermore, we extended the iterative methodology by the use of a new functionalized DPE derivative, 1-(3-chloromethylphenyl)-1-((3-(1-phonyletheny1)phenyl) ethylene, capable of introducing two DPE functionalities via one DPE anion reaction site in the reaction (b). The number of arm segments of the star-branched polymer synthesized by the methodology could be dramatically increased to 2, 6, and up to 14 by repeating the iterative process.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1771-1776
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• 2007

The synthesis of well-defined dendrons based on aliphatic polyether dendritic cores and glassy polystyrene peripheries is described. The synthetic route involves a combination of living anionic polymerization and a stepwise convergent method consisting of iterative Williamson etherification and hydroboration/oxidation reactions. On the basis of molecular weight, as characterized by gel permeation chromatography (GPC), the first generation dendron (Generation-1) shows a random coil conformation like a linear polystyrene, while higher generations (Generation-2 and 3) reveal globular forms in solution.

• Proceedings of the Polymer Society of Korea Conference
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• 2006.10a
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• pp.332-332
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• 2006

Well difined sulfonated styrene and n-butyl acrylate (nBA) block copolymers were synthesized by CuBr catalyzed living radical polymerization followed by acification by thermolysis. Neopentyl styrene sulfonate (NSS) was polymerized with PnBA macroinitator precursor ($M_{n}=19,500,\;PDI\;<\;1.09$) and CuBr catalyst with N,N,N',N' -pentamethylethyleneamine (PMDETA) to give nBA-NSS block copolymer with narrow polydispersity ($M_{n}=29,900,\;PDI\;<\;1.15$). PNSS segments in the block copolymer were then acidified by thermolysis at $150^{\circ}C$ resulting in polystyrene segments with 100 % sulfonic acid groups.

• 제어로봇시스템학회:학술대회논문집
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• 1993.10a
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• pp.766-771
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• 1993

A mathematical model is developed to represent the batch reactor for free radical polymerization of PMMA The model is validated by comparing the simulation result with the experimental data. A computational scheme is proposed to determine the trajectory of the reactor temperature that will produce polymer product having the desired molecular weight distribution. For this instantaneous number average chain length and polydispersity are introduced to calculate the reactor temperature. The former is assumed to be a second order polynomial of the sum of the living and dead polymer concentrations. Various reactor temperature, trajectories are observed depending on the reactor conditions and prescribed molecular weight distributions. Fuzzy and PID control algorithms are applied to trace the reactor temperature trajectory. While the PID control gives rise to an overshoot when the trajectory changes its direction, the fuzzy controller yields a more satisfactory performance because it secures information on the trajectory pattern.

• Proceedings of the Korean Fiber Society Conference
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• 2001.10a
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• pp.223-226
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• 2001

비닐에테르류의 비닐단량체는 ZnI$_2$ 존재하에서 HI와 같은 프로톤 산에 의해 양이온 리빙중합이 가능함이 보고된 바 있는데 이 때 프로톤산은 비닐에테르 단량체와 반응하여 adduct를 생성하고, ZnI$_2$는 adduct의 양이온중합 활성화제로 작용하는 것으로 알려져 있다. (중략)