• Applied Chemistry for Engineering
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• v.2 no.3
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• pp.199-208
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• 1991

Carbocationic polymerization is widely applied to prepare polymers from electron-rich monomers. The reaction is usually uncontrollable due to many side reactions and explosively fast rate of polymerization. In a living polymerization, however, the reaction is controlled as designed, and many workers reported many successful cases recently. In this review several ways of living carbocationic polymerization were illustrated, and they were connected together under a basic principle.

• Macromolecular Research
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• v.13 no.3
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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.

• Fibers and Polymers
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• v.2 no.1
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• pp.131-134
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• 2001

Living cationic polymerization behaviors of isobutyl vinyl ehters (IBVE), initiated by iodomethyl methyl ether (IMME)/zinc iodide ($Znl_2$) have been investigated. The polymerization was carried out at 0, -15, and $-30^{\circ}C$ in toluene. It was found that the rate of polymerization increased as the IMME concentration increased and decreased as temperature decreased. 100% conversion was always achieved without exception. Furthermore, the number-average molecular weight ($M_{n}$) of polymers increased in direct proportion to monomer conversion. The molecular weights of polymers were in good agreement with the theoretical values, calculated on the basis that one polymer chain was formed by one IMME molecule and the values of polydispersity index are always less than 1.2, revealing the living nature. The living nature was also confirmed by synthesis of poly(IBVE-b-TBVE) by subsequent monomer addition of t-butyl vinyl ether (TBVE).

• Macromolecular Research
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• v.17 no.1
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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.

• Proceedings of the Korean Fiber Society Conference
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• 2003.10a
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• pp.1-2
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• 2003

Some new synthetic routes for the preparation of poly (isobutyl vinyl ether) (P(IBVE)) having a controllable molar mass with narrow distribution via catalytic or photoinduced living cationic polymerization and their conversion to corresponding PVA have been developed. It was found that the combination of iodomethyl methyl ether (IMME)-zinc iodide is effective in the initiation of the catalytic and the various combinations of diphenyliodonium halides, well known photocationic initiators (DPIX) with zinc halides (ZnX$_2$) are also useful in photoinduced living cationic polymerization of isobutyl vinyl ether (IBVE). Polymerization both in the catalytic and photoinduced systems precede until the full consumption of the monomer and the rate of polymerization increases as the concentration of the catalyst or photoinitiator. The number average molar mass of the resulting polymer is proportional with % conversion, which is determined by the ratio of monomer consumed and the initial values of the catalyst or initiator. The living nature was also confirmed by subsequent monomer addition technique.

• Fibers and Polymers
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• v.5 no.4
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• pp.253-258
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• 2004

Living nature of photoinduced cationic polymerization of isobutyl vinyl ether (IBVE) in the presence of various combinations of diphenyliodonium halide (DPIX), a photocationic initiator and zinc halide $(ZnX_2)$ in methylene chloride has been investigated. Attainment of $100\%$ conversion and a linear relationship between $\%$conversion and number average molar mass of the resulting polymer, strongly suggests the living nature of this system. Livingness of the polymerization system was observed irrespective to the type of halide anion of the initiator and zinc salts unless the reaction temperature is not higher than $-30^{\circ}C$. The rate of polymerization decreases in the order of iodide > bromide > chloride when halide salt of DPIX and $ZnX_2$ are used. It is postulated that the cationic initiation is started by the insertion of weakly basic monomer in to the activated C-X terminal of the monomer adduct which is a reaction product of monomer and HX, a photolytic product of DPIX, formed in situ during the photo-irradiation process. It was concluded that polymerization is initiated by the insertion of weakly basic monomer into activated C- X terminal of monomer adduct due to the pulling action of$ZnX_2$, which successively producing a new polarized C-X terminal for the propagation in cationic nature. This led us to a conclusion that the living nature of this cationic polymerization is ascribable to the polarized C-X growing terminal, which is stable enough to depress the processes of chain transfer or termination process.

• Macromolecular Research
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• v.16 no.2
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• pp.155-162
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• 2008

We report the successful synthesis of poly(NBECOOH-b-NBEPOSS) copolymers, taking advantage of the sequential, living ring opening metathesis polymerization of NBETMS and NBEPOSS using the $RuCl_2(=CHPh)(PCY_3)_2$/$CH_2Cl_2$/$20^{\circ}C$ system, followed by the hydrolysis of trimethylsilyl groups in poly(NBETMS-b-NBEPOSS) copolymers. The living behavior of ROMP of NBETMS was first investigated using two diagnostic plots, a first order kinetic plot and a $\bar{M}_n$ vs. conversion plot. The plots confirmed that no termination and chain transfer reaction had occurred during polymerization. Poly(NBECOOH-b-NBEPOSS) copolymers were prepared using the sequential monomer addition of NBEPOSS to living poly(NBETMS) chain ends, followed by the hydrolysis of trimethylsilyl groups in the poly(NBETMS-b-NBEPOSS) copolymers. The high structural integrity of poly(NBE-COOH-b-NBEPOSS) copolymers was confirmed by $^1H$-NMR, $^{13}C$-NMR spcctroscopy and GPC.

• Macromolecular Research
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• v.13 no.5
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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.

• Elastomers and Composites
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• v.44 no.3
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• pp.209-221
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• 2009

Polyolefins are important commodity polymers with the largest volume of business owing to their outstanding combination of cost performance and excellent physical properties. However, the lack of functional groups often has limited their end uses, such as compatibilizer, modifier and adhesive, where the interaction with other materials is especially important. The incorporation of functional groups as polymer segments to afford block or graft polyolefin copolymers has been extensively investigated in the context of the functional polyolefin hybrids. Living polymerization processes have been considered to be an efficient method to prepare the polyolefin hybrids with precisely controlled architecture and compositions. Among the living polymerization techniques, controlled/"living" radical polymerization (CRP) methods are very effective not only because of the controllability of polymerization but also because of the versatility of monomers and polymerization conditions. In this review paper, progresses on the preparations of polyolefin graft or block copolymers through CRP techniques are summarized. The commodity polymers such as polyisobutylene, polyethylene and polypropylene are combined with polar segments such as polyacrylate, polymethacrylate, polystyrene to yield functionalized polyolefins.

• Macromolecular Research
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• v.13 no.3
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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.