• Macromolecular Research
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• 제13권3호
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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.

• Elastomers and Composites
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• 제44권1호
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• pp.55-62
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• 2009

본 논문에서는 nitroxide 매개 리빙라디칼 중합법을 이용한 isoprene의 중합 특성에 관하여 연구하였다. 중합 첨가제로 acetol이 첨가된 경우, 생성되는 고분자의 분자량이 전환율에 따라 직선적으로 증가하고, 제조된 고분자의 분자량 분포값이 1.5 이하의 값을 보임으로써, 성공적인 리빙라디칼 중합이 이루어졌음을 알 수 있었다. 제조된 polyisoprene은 약 22%의 3, 4구조, 약 30%의 1, 4-cis구조, 약 48%의 1, 4-trans 구조로 구성되어 있었다. 중합은 145 $^{circ}C$에서 최선의 결과를 보였으며, 이보다 낮은 온도에서는 진행되지 않았다. Nitroxide의 경우, non-cyclic nitroxide인 di-tert-butyl nitroxide (DTBN)의 경우 리빙라디칼 중합을 매개하지 못하였으나, 2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (TEMPO)와 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (oxoTEMPO)의 경우 성공적으로 리빙라디칼 중합을 매개하였다. 그러나, 주어진 중합조건 내에서 일부 isoprene은 Diels-Alder 이량화 반응(dimerization)에 의하여 고분자가 아닌 limonene 등으로 전환되는 것으로 관찰되었다. 주어진 중합조건하에서 isoprene의 자동열개시 반응도 가능하였으나, 별도의 중합개시제를 사용할 경우 그 정도는 무시할 수 있을 정도의 양인 것으로 판단되었다.

• Macromolecular Research
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• 제15권4호
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• pp.324-329
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• 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.

• 폴리머
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• 제34권6호
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• pp.553-559
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• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.337-337
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• 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.

• 접착 및 계면
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• 제9권4호
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• pp.30-33
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• 2008

블락 고분자 박막과 기판 사이의 계면에 1 nm 두께의 얇은 단일 성분 고분자 나노 계면을 도입함으로써 블락 고분자 나노 구조의 배향을 조절하는 연구가 수행되었다. Polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA) 블락 고분자 박막의 나노 구조를 조절하기 위하여 블락 고분자의 각각의 고분자들의 평균 조성을 가지며 한쪽 끝에 히드록시 기를 가지는 단일 성분 고분자인 폴리(4-아세톡시스티렌) (OH-PAS)과 폴리(4-메톡시스티렌) (OH-PMS)를 나이트록사이드를 이용한 라디칼 중합법(nitroxide-mediated radical polymerization, NMP)을 사용하여 성공적으로 합성하였다. 실리콘 웨이퍼 표면과 저압 탈수 반응을 통하여 OH-PAS와 OH-PMS 두 개의 고분자를 성공적으로 표면에 공유결합 하였으며 생성된 두 고분자가 결합된 1 nm 두께의 계면 위에 PS-b-PMMA 블락 고분자 박막을 도포하여 그 나노 구조의 배향을 분석하였다. OH-PMS를 사용하여 제작된 계면의 경우 블락 고분자에 대하여 약 30%의 수직 배향을 보여주었고 OH-PAS를 사용하여 제작된 계면의 경우 수직 배향을 전혀 보여주지 않았고 오직 수평 배향만을 보여주었다. 결과적으로 계면의 화학적 조성을 정밀하게 조절하는 것이 블락 고분자 박막의 나노 구조 배향을 조절하는 데 가장 중요한 요소라고 고려된다.

• Macromolecular Research
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• 제13권3호
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• pp.187-193
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• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.95-96
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• 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
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• 제32권7호
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• pp.2377-2384
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• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.318-318
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• 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.