• Journal of the Korean Chemical Society
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• v.24 no.3
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• pp.259-265
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• 1980

Poly (styrene-b-methyl methacrylate) (PS-b-PMMA) was synthesized by free radical telomerization: the telomerization of styrene with $CCI_4$ by using AIBN as initiator followed by a second telomerization of methyl methacrylate using $CCI_3$ end group of the resulting polymer as the macrotelogen, with AIBN initiation, gave the styrene-methyl methacrylate block copolymer. The effects of the concentration of the macrotelogen, the concentration of monomer, the molecular weight of the macrotelogen, the reaction temperature and the concentration of the solvent on the formation of the block copolymer were investigated. Block copolymers containing up to 10 weight percent PMMA were obtained by adjusting the reaction conditions.

• Journal of the Korean Chemical Society
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• v.6 no.1
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• pp.88-93
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• 1962

The telomerization of vinyl acetate with carbon tetrachloride, chloroform and monochlorobenzene were investigated with respect to the synthesis of those telomers, properties and molecular weights of the formed telomers, and reaction mechanisms. Vinyl acetate reacted with carbon tetrachloride and chloroform to form telomers at 70-90$^{\circ}C$ and 60-70$^{\circ}C$, respectively and it formed polymer with monochlorobenzene. As a chain transfer agent, carbon tetrachloride was more effective than chloroform. In the telomerization of vinyl acetate and carbon tetrachloride: 1) The average molecular weight of the telomer decreased as the mole ratio of carbon tetrachloride to vinyl acetate increased. The optimum conditions for the highest yield of the telomer were as follows: Mole ratio of carbon tetrachloride to vinyl acetate : 2.5 Reaction time : 20 hours. 2) As the reaction proceeded, the refractive index and average molecular weight of the telomer increased rapidly in the first 10 hours but the increase was slow through the next 10 hours, so that, the average recurring number(n) of taxogen in the final product reached an almost definite value, i.e., 3. The telomer formed in the telomerization of vinyl acetate with carbon tetrachloride and chloroform turned to brown color in the air due to decomposition or polymerization. The suggested telomerization mechanism was supported by the hexachloroethane detected in the course of reaction.

• Polymer(Korea)
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• v.27 no.1
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• pp.26-32
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• 2003

Poly(vinyl pivalate)(PVPi) telomer containing bifunctional end groups was synthesized through radical telomerization of vinyl pivalate. The number-average molecular weight ($\bar{M}$n) of the synthesized telomers was investigated by GPC, $^1$H-NMR, and viscometric methods. PVPi telomers having a number-average molecular weight ($\bar{M}$n) of 2400~1300 g/mol were obtained. In order to control the molecular weight of telomers, chain transfer constants ($C_s$) of telogen ($CCl_4$) were determined by using the Mayo equation and simulation, which were 1.15, 1.16, and 1.18 at 40, 50, and 6$0^{\circ}C$, respectively. $\bar{M}$n of the synthesized telomers at 6$0^{\circ}C$ were between 5100 and 5400 g/mol at conversion of increasing from 18 to 72%. Those are corresponding to simulation results.

• Macromolecular Research
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• v.10 no.6
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• pp.339-344
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• 2002

Poly(vinyl alcohol-b-styrene) (poly(VA-b-St)) diblock copolymer containing high syndiotactic poly (vinyl alcohol) (PVA) was synthesized by the saponification of poly(vinyl pivalate-b-styrene) (poly(VPi-b-St)). For the block copolymer, poly(vinyl pivalate) (PVPi) with trichloromethyl end group was obtained via telomerization of vinyl pivalate with carbon tetrachloride as a telogen and 2,2-azobisisobutyronitrile (AIBN) as an initiator. Then resulting poly(vinyl pivalate) with trichloromethyl end group was used as an effient macroinitiator for the synthesis of poly(VPi-b-St) using atom transfer radical polymerization (ATRP) in the presence of CuCl/2,2'-bipyridine at 130 $^{\circ}C$. The poly(vinyl pivalate) macroinitiator, poly(VPi-b-St), poly(VA-b-St) were characterized by GPC, FT-IR and $^1$H-NMR. And the analysis showed that integrity of the block copolymer was maintained during saponification reaction.

• Proceedings of the Korean Fiber Society Conference
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• 2002.04a
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• pp.37-40
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• 2002

폴리비닐알콜(Poly(vinyl alcohol)(PVA))은 매우 넓은 온도 범위에서 물에 쉽게 용해될 수 있는 친수성 고분자로 우수한 생체적합성을 가진 합성고분자 중에 하나이다[1]. 이러한 PVA는 단량체의 호변이성질화로 인하여 대부분 알데하이드 형태로 존재하기 때문에 비닐에스테르계열의 단량체를 중합하여 비누화시켜 제조하는 것이 일반적인 방법으로 알려져있다[2]. 최근 생체적합성을 가진 합성고분자에 대한 관심이 부각되면서 PVA에 대한 연구가 활발히 진행되고 있는데, 이는 PVA가 다른 합성고분자에 비하여 비교적 구조가 간단하고, 또한, 측쇄에 존재하는 수산기에 의하여 다양한 물성을 나타내기 때문이다. (중략)

• Bulletin of the Korean Chemical Society
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• v.1 no.2
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• pp.45-49
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• 1980

During the homolytic reactions of $CCl_4$ or $Cl_3CBr with ${\beta}-halo^1$-styrenes,$\beta$-haloradicals are key intermediates. They are to be stabilized via three pathways; $\beta$-cleavage, halogen transfer and telomerization. The three reaction paths are delicately controlled by the energetics of their formation and stabilization. When the formation of a $\beta$-haloradical is accompanied by considerable excess of energy from an exothermic reaction, $\beta$ -cleavage is often dominant over the halogen transfer. On the other hand, if the radical forms via a reversible reaction, two processes become competitive. $\beta$-Eliminated bromine atoms from ${\beta}$ -bromoradicals generate $Br_2$ via $Cl_3CBr + {\cdot}Br {\leftrightarrow} Br_2 + {CCl_3}{\cdot}{Br_2}$ may act as a better scavenger than Cl3CBr for the ${\beta}$-bromoradicals. Different reactivities of chlorine, bromine and trichloromethyl radicals towards olefinic pi-bond are clarified in terms of the beat content of the addition reactions.

• Macromolecular Research
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• v.17 no.8
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• pp.557-562
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• 2009

The free radical polymerization of styrene was initiated with azobis(isobutyronitrile) in the presence of benzene sulfonyl chloride. Analysis of the terminal structures of the obtained polystyrene with $^1H$ NMR spectroscopy revealed the presence of a phenyl sulfonyl group at the ${\alpha}$-end and a chlorine atom at the ${\omega}$-end of each polystyrene chain. The terminal chlorine atom in the polystyrene chains was further confirmed through atom transfer radical polymerization (ATRP) of styrene and methyl acrylate using the obtained polystyrenes as macroinitiators and CuCl/2,2'-bipyridine as the catalyst system. GPC traces of the products obtained in ATRP at different reaction times were clearly shifted to higher molecular weight direction, indicating that nearly all the macroinitiator chains initiated ATRP of the second monomers. In addition, the number-average molecular weights of the polystyrenes increased directly proportional to the monomer conversions, and agreed well with the theoretical ones.