• Macromolecular Research
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• 제13권3호
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• pp.236-242
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• 2005

Three dithioester-derived carboxyl acid functionalized RAFT(reversible addition-fragmentation chain transfer) agents, viz. acetic acid dithiobenzoate, butanoic acid dithiobenzoate and 4-toluic acid dithiobenzoate, were used in the RAFT bulk polymerization of styrene, in order to study the effects of the R-group structure on the living nature of the polymerization. By conducting the polymerization with various concentrations of the RAFT agents and at different temperatures, it was found that the R-group structure of the RAFT agents plays an important role in the RAFT polymerization; the bulky structure and radical stabilizing property of the R-group enhances the living nature of the polymerization and allows the polymerization characteristics to be well controlled.

• 통합자연과학논문집
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• 제5권2호
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• pp.127-130
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• 2012

Polymerization of vinyl monomers is promoted by thianthrene cation radical as a part of our research concerning the reactions of various agents with readily isolable, yet highly reactive species and elucidate the biological activity. Thianthrene cation radical initiated the homopolymerization and copolymerization of styrene and ethyl vinyl ether. The polymerization yields decreased as the concentration of phenylacetylene or diphenylethylene increased. Such polymereization by cationic thianthrene radical could provide some clues for the reaction in living animals. Comments on possible polymerization mechanisms were suggested.

• Elastomers and Composites
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• 제44권3호
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• pp.209-221
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• 2009

폴리올레핀은 뛰어난 물성과 낮은 가격으로 인하여 가장 큰 시장을 가진 범용 고분자이다. 그러나, 폴리올레핀은 대표적인 비극성 고분자로, 다른 물질과의 상호 작용이 중요한 상용화제, 개질제, 접착제 등의 용도로는 그 사용이 제한될 수 밖에 없다. 따라서, 보다 극성을 가진 고분자 사슬을 폴리올레핀에 블록 또는 그라프트 공중합체의 형태로도입함으로써 기능성 폴리올레핀 하이브리드를 제조하려는 노력이 계속되어 왔다. 특히, 잘 제어된 구조와 조성을 가진 공중합체를 제조하기 위하여 리빙라디칼 중합법이 사용될 수 있으며, 그 중 조절라디칼 중합법은 중합을 잘 제어할 수 있다는 장점 이외에 다양한 단량체종과 중합 공정에 적용될 수 있다는 점에서 많은 주목을 받고 있다. 이에 따라, 본 리뷰 논문에서는 조절라디칼 중합법을 이용한 폴리올레핀 기반 블록 또는 그라프트 공중합체의 제조에 대하여 정리해 보았다. 폴리이소부틸렌, 폴리에틸렌, 폴리프로필렌 등의 비극성 범용고분자들과 폴리아크릴레이트, 폴리메타아크릴레이트, 폴리스티렌 등의 극성 고분자들과의 하이브리드를 통한 기능성 폴리올레핀의 제조에 대하여 정리하였다.

• 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.

• 한국고분자학회:학술대회논문집
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• 한국고분자학회 2006년도 IUPAC International Symposium on Advanced Polymers for Emerging Technologies
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• pp.93-94
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• 2006

This lecture will present an overview of recent advances in our transition metal-mediated living radical polymerization, particularly focused on catalyst design and precision synthesis of functional polymers. Selected topics will include: (A) Design of Transition Metal Complexes: Evolution of Catalysts (B) New Ruthenium and Iron Catalysts: Active and Versatile (C) Functional Methacrylates for Advanced Functional Polymers (D) Functional Star Polymers: Microgel Cores for Metal Catalysts.

• Macromolecular Research
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• 제13권5호
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• pp.391-396
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• 2005

The polymerization of methyl methacrylate (MMA) was carried out using CuBr/bidentate phosphorus ligand catalyst systems. MMA polymerization with CuBr/phosphine-phosphinidene (PP) exhibited high conversion ($\~80\%$) in 5 h at $90^{\circ}C$ along with a linear increase of ln($[M]_0/[M]$) versus time, indicating constant concentration of the propagating radicals during the polymerization. The molecular weight of the prepared PMMA tended to increase with conversion, suggesting the living polymerization characteristic of the system. On the other hand, a large difference between the measured and theoretical molecular weight and a broad molecular weight distribution were observed, implicating possible incomplete control over the polymerization. This may have been caused by the low deactivation rate constant ($\kappa_{deact}$) of the system. The low $\kappa_{deact}$, would result in irreversible generation of radicals instead of reversible activation/deactivation process of ATRP. Polymerizations performed at different ligand to CuBr ratios and different monomer to initiator ratios did not afford better control over the polymerization, suggesting that the controllability of CuBr/phosphorus ligand system for ATRP is inherently limited.

• Macromolecular Research
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• 제17권1호
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• pp.14-18
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• 2009

The acceleration effect of various organic acids, such as methanesulfonic acid (MSA), ethanesulfonic acid (ESA), 4,4'-sulfonyldibenzoic acid (SDA), diphenylacetic acid (DPAA), and $\rho$-toluenesulfonic acid (TSA), on the rate of styrene bulk polymerization with 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and benzoyl peroxide (BPO) was investigated. The addition of organic acids significantly accelerated the rate. Among these organic acids, DPAA showed an efficient rate-accelerating effect with living nature of polymerization. When DPAA was used as a rate-accelerating additive for TEMPO-mediated living free radical polymerization (LFRP), the rate of polymerization was dramatically enhanced, the linearity of reaction kinetics was successfully maintained, and the polydispersity was effectively controlled.

• Macromolecular Research
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• 제15권4호
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• pp.302-307
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• 2007

The living radical polymerization of methyl methacrylate (MMA) by atom transfer radical polymerization, (ATRP) employing a $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine (PyP) catalytic system (X=Cl, Br), was investigated using several initiators and solvents at various temperatures. Most of the polymerizations with the PyP ligand were well controlled, with a linear increase in the number average molecular weights ($M_n$) vs. conversion, with relatively low molecular weight distributions ($M_w/M_n=1.2-1.4$) throughout the reactions. The measured weights matched those of the predicted values. The ethyl-2-bromoisobutyrate (EBriB) initiated ATRP of MMA, with the $Fe(II)X_2/diphenyl-2-pyridyl$ phosphine catalytic system (X=Cl, Br), was better controlled in p-xylene at $80^{\circ}C$ than the other solvents used in this study.

• 한국응용과학기술학회지
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• 제26권3호
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• pp.306-316
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• 2009

In this study, block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) by ATRP(atom transfer radical polymerization) method was synthesized. 4 arm-molecule which contained halogen atom was synthesized for an initiator. With 4 arm-molecule monodispered polystyrene were synthesized by ATRP method. The molecular change of synthesized monodispersed polystyrene with respect to time was investigated and living polymer characteristic was confirmed. Block copolymer of polystyrene and polyethylene glycol methyl ether methacrylate(PEGMA) was synthesized by ATRP with macroinitiator which was synthesized from the monodispersed polystyrene(Mn=12000). The molecular weight of obtained PS-b-PEGMA was 22,000.

• 통합자연과학논문집
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• 제6권2호
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• pp.71-75
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• 2013

$Bu_3Sn$-endded poly(vinyl)s with biological activity were obtained by the radical polymerization of vinyl monomers using thianthrene cation radical/$^nBu_3H$. Thianthrene cation and stannyl radicals promoted the homopolymerization and copolymerization of styrene and ethyl vinyl ether having number average molecular weights of 2000-3100. Tributyltin hydride functions as a chain transfer agent. Such polymereization by cationic thianthrene and stannyl radicals could provide some clues for the biological reaction in living animals. Plausible polymerization mechanisms were suggested.