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

• Elastomers and Composites
• /
• v.44 no.1
• /
• pp.55-62
• /
• 2009

In this study, investigation on the polymerization characteristics of isoprene through nitroxide mediated controlled/"living" radical polymerization techniques was attempted. In the presence of acetol, linear increase of isoprene conversion with time and low polydispersities of the resulting polymers ($M_w/M_n$ < 1.5) were observed, which suggest successful controlled/"living" radical polymerization of isoprene. The microstructure of the resulting polyisoprene was composed of $\sim$ 22% of 3, 4, $\sim$30% of 1, 4-cis and $\sim$ 48% of 1, 4-trans. The optimum polymerization temperature was 145 $^{circ}C$, below which no significant polymerization behavior was observed. Non-cyclic nitroxide, such as di-tert-butyl nitroxide (DTBN) could not mediate the polymerization, whereas cyclic nitroxides (2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (TEMPO) and 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (oxoTEMPO)) were successfully employed for the polymerization. However, isoprene dimerization reaction through Diels-Alder process was also observed at the given polymerization condition, which afforded a significant amount of limonene. Isoprene thermal autoinitiation was also possible, which was, however, considered to be not significant under the given polymerization condition.

• Macromolecular Research
• /
• v.15 no.4
• /
• pp.324-329
• /
• 2007

An octa-functional alkoxyamine initiator, with the 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO) free radical, was synthesized based on resorcinarene, with its efficiency to initiate the nitroxide-mediated free radical copolymerization of styrene and methyl methacrylate (MMA) described. A difunctional analogue of this initiator was also synthesized, using resorcinol as the core molecule. The structures of the resulting initiators were confirmed by homolysis studies based on electron spin resonance spectroscopy and molecular modeling. The polymerization behavior and characteristics of the polymers obtained using these two initiators were also compared. Well-defined star-shaped and linear random copolymers, with low polydispersities and controlled molecular weights, were prepared. The efficiencies of these initiators towards copolymerization, as well as the parameters permitting the formation of well-defined polymers, were also investigated. The reactivity ratios were $r_a=0.42(a=styrene)\;and\;r_b=0.33(b=MMA)$ for the octa-functional initiator system and $r_a=0.45\;and\;r_b=0.39$ for the difunctional initiator system.

• Polymer(Korea)
• /
• v.34 no.6
• /
• pp.553-559
• /
• 2010

The paper describes the preparation and characterization of conductive polyaniline-modified polymers by growing of aniline onto functionalized poly(styrene-co-p-methylstyrene) [P(St-co-MSt)]. For this purpose, P(St-co-MSt) was synthesized via nitroxide mediated radical polymerization (NMRP) and then N-boromosuccinimide was used for introduction of bromine to the benzylic positions of copolymer. Afterwards, 1,4-phenylenediamine was linked to the brominated P(St-co-MSt) and functionalized copolymer $[P(St-co-MSt)-NH_2]$ was prepared. The graft copolymerization of aniline monomers onto functionalized P(St-co-MSt) was initiated by oxidized phenylamine groups after addition of ammonium peroxydisulfate (APS), and p-toluenesulfonic acid-doped PANI was chemically grafted onto P(St-co-MSt) via oxidation polymerization. The obtained terpolymer was studied by FTIR and UV-Vis spectroscopy and its thermal behaviour were examined by DSC and TGA analyses. The conductivity of terpolymer was measured by four-point probe method and electroactivity was measured by cyclic voltammetry (CV). The solubility of P(St-co-MSt)-g-PANI was examined in common organic solvents.

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.337-337
• /
• 2006

The synthesis of an octafunctional resorcinarene based initiator for nitroxide mediated polymerization and its ability to yield random star copolymers of styrene and methyl methacrylate is studied. The effect of the initiator conformations towards its activity and the conditions that permit the formation of well-defined star block copolymers is also investigated in detail. The characterization of the initiator and the polymers were carried out by various spectro-analytical techniques. Well-defined random copolymers were obtained with controlled molecular weight and low PDI depending on the monomer feed.

• Journal of Adhesion and Interface
• /
• v.9 no.4
• /
• pp.30-33
• /
• 2008

Two polymeric interfaces with single component homo-polymers were prepared to control the orientation of block copolymer thin-film nanostructures. Poly(4-acetoxy styrene) (OH-PAS) and poly(4-methoxy styrene) (OH-PMS) which have the average chemical composition of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) were precisely synthesized through nitroxide-mediated radical polymerization. After dehydration reactions between above polymers and SiOx layers of silicon wafers, the polymer-modified interface induced partial (30%) vertical orientation of PS-b-PMMA thin film in the case of OH-PMS and wholly parallel orientation in the case of OH-PAS. Chemical compositions of polymeric interface layers are regarded as the key parameter to control the orientation of nanostructures of block copolymer thin film.

• Macromolecular Research
• /
• v.13 no.3
• /
• pp.187-193
• /
• 2005

The TEMPO-mediated living free-radical bulk and dispersion polymerization of styrene in the presence of camphorsulfonic acid (CSA) are investigated. In the absence of TEMPO and CSA in the bulk polymerization, a conversion of $93\%$ is achieved within 6 hr of polymerization. When only TEMPO is involved in this polymerization, the pseudo-living free-radical polymerization is well achieved, however, the polymerization rate becomes quite slow. This retardation of the polymerization rate is solved by the addition of a low concentration of CSA. In the TEMPO-mediated dispersion polymerization in the presence of CSA, similar trends in the conversion, kinetics, and PDI are observed as those observed in the case of bulk polymerization. When only TEMPO is used in the dispersion polymerization, the resulting particle size becomes quite broad, due to the prolonged polymerization time. However, when a 1.0 molar ratio of CSA to TEMPO is added to the TEMPO-mediated dispersion polymerization, fairly mono-disperse PS microspheres having an average size of 5.83 $\mu$m and a CV of 3.4$\%$ are successfully obtained, due to the narrow molecular weight distribution of the intermediate oligomers and shortening of the polymerization time. This result indicates that the addition of CSA to the TEMPO-mediated bulk and the use of dispersion polymerization not only shortens the polymerization time, but also greatly improves the uniformity of the microspheres.

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.95-96
• /
• 2006

Surface modification of clay minerals has become increasingly important for improving the practical applications of clays such as polymeric nanocomposites. We used the copolymer as modifiers having phenyl components, and successfully developed a route for the preparation of amine functionalized polymer based on oligostyrene and its block copolymers. The oligo(St-co-VBC)s with controlled molecular weight were synthesized via nitroxide mediated polymerization method. We also successfully prepared organophilic layered silicates whose surface is covered with styrenic copolymers. Through the analysis of chemical structure and morphology, we concluded that copolymers were very effective organic modifiers to change the surface characteristics of layered silicates.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.7
• /
• pp.2377-2384
• /
• 2011

Azo-acenaphthylene oligomers with repeating acenaphthylene units "n" up to 4, 5, 7, 17 and 19 have been prepared successfully using nitroxide mediated Stable Free Radical Polymerization (SFRP). Azo-acenaphthylene oligomers, reversibly end-capped by the stable nitroxide 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO), were further reacted via radical addition to 4-(naphthalenemethoxy)styrene monomer for diblock co-polymer formation. Characterization of the oligomers and diblock co-polymers was accomplished using MALDI-MS supported by GPC (Gel Permeation Chromatography) and $^1H$ NMR spectrometry. MALDI-MS afforded definitive results by providing an inter-peak interval of 152 (m/z), corresponding to acenaphthylene monomer, and inter-peak interval of 260 (m/z) for the naphthalenemethoxystyrene monomer unit in block copolymers. Our study opens the way to control the number of repeat units in the oligomers. Further these oligomers can be tailored with various monomers for the formation of block copolymers.

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.318-318
• /
• 2006

4-Vinylbenzyl maltohexaoside peracetate, 1, was copolymerized with divinylbenzene using the initiator for nitroxide-mediated living radical polymerization, 2, to afford the polystyrene microgel with acetyl maltohexaose, 3. The deacetylation of 3 was achieved by treatment with sodium methoxide in dry 1,4-dioxane to produce the polystyrene microgel with maltohexaose, 4. A good coating property of the polystyrene microgel was combined with an excellent hydrophilic property derived from maltohexaose. In addition, 4 showed the ability to solubilize fullerene in aqueous solution. Therefore, 4 has a potential application as a special coating using functional but incompatible compounds such as fullerene on the surface of various hydrophilic materials.