• Title/Summary/Keyword: chain transfer to polymer

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Chain Transfer to Monomer and Polymer in the Radical Polymerization of Vinyl Neo-decanoate

  • Balic, Robert;Fellows, Christopher M.;Van Herk, Alex M.
    • Macromolecular Research
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    • v.12 no.4
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    • pp.325-335
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    • 2004
  • Molecular weight distributions of poly(vinyl neo-decanoate) produced by the bulk polymerization of the monomer to low conversions were investigated to obtain values of the rate constants for the chain transfer to monomer ( $C_{M}$). The value of $C_{M}$ of 7.5($\pm$0.6)${\times}$10$^{-4}$ was obtained from a logarithmic plot of the number distribution at 5,25, and 5$0^{\circ}C$, which suggests that the activation energy for chain transfer is on the order of 20-25 kJ ㏖$^{-1}$ . These plots were linear between the number and weight-average degrees of polymerization, but not over the whole molecular weight range for which a significant signal was observed in the gel permeation chromatography (GPC) trace. Modeling suggests that the deviations observed at high molecular weights can be explained by branching of the chains through chain transfer to the polymer, with a branching density as low as 10$^{-5}$ , without affecting the slope at low values of the number of monomer unit, N. This deviation from the expected distribution of linear chains was used to estimate the branching densities at low conversion.ion.

Transfer Matrix Algorithm for Computing the Geometric Quantities of a Square Lattice Polymer

  • Lee, Julian
    • Journal of the Korean Physical Society
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    • v.73 no.12
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    • pp.1808-1813
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    • 2018
  • I develop a transfer matrix algorithm for computing the geometric quantities of a square lattice polymer with nearest-neighbor interactions. The radius of gyration, the end-to-end distance, and the monomer-to-end distance were computed as functions of the temperature. The computation time scales as ${\lesssim}1.8^N$ with a chain length N, in contrast to the explicit enumeration where the scaling is ${\sim}2.7^N$. Various techniques for reducing memory requirements are implemented.

Preparation of Acryl Binder with Silane Type Chain Transfer Agent (실란계 사슬 이동제를 사용한 아크릴 바인더의 제조)

  • Kim, Jin-Gon;Shin, Min-Jae;Shin, Jae-Sup
    • Polymer(Korea)
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    • v.36 no.3
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    • pp.351-356
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    • 2012
  • Acryl binder is a representative organic additive for the manufacture of the display electronic equipment. Acryl binder is usually synthesized by radical copolymerization. Glycidyl methacrylate (GMA), methyl methacrylate (MMA), and methacrylic acid (MAA) were used in this copolymerization of acryl binder. In this study the silane type mercaptane compound was used as a chain transfer agent (CTA) to enhance the adhesion property of the acrylic binder. The CTA used in this experiment was (3-mercaptopropyl) trimethoxysilane (MPTMS). Molecular weight of the copolymer, thickness of the coating, transmittance, and adhesion property were measured. The molecular weight was controlled and the adhesion property was improved by using this silane type chain transfer agent.

Xanthate-Mediated Controlled Radical Polymerizations of N-Vinylcarbazole and Synthesis of Star Polymers

  • Mori, Hideharu;Ookuma, Hiroshi;Endo, Takeshi
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.322-322
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    • 2006
  • Well-defined poly(N-vinylcarbazole), poly(NVC), was synthesized by macromolecular design via interchange of the xanthate (MADIX)/reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of a suitable xanthate-type chain transfer agent (CTA). Good control of the polymerization was confirmed by the linear first-order kinetic plot, the molecular weight controlled by the monomer/CTA molar ratio, linear increase in the molecular weight with the conversion, and the ability to extend the chains by the second addition of the monomer. Star polymers having various architectures were also synthesized using this technique.

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Characteristics and Ring-Opening Isomerization Polymerization of 2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) (2-(1,3,3-Trimethyl-6-azabicyclo[3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline(TAO)의 개환이성화중합과 특성평가)

  • Lee, Chan-Woo;Chung, Jin-Do
    • Polymer(Korea)
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    • v.36 no.3
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    • pp.262-267
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    • 2012
  • 2-(1,3,3-Trimethyl-6-azabicyclo [3,2,1]-oct-6-yl)-4,5-dihydro-1,3-oxazoline (TAO) was polymerized at several conditions to clarify the influence of initiators, alkyl halide ($PhCH_2Br$, $PhCH_2Cl$, MeI) and sulfonate (MeOTf). The reactions were conducted at $100^{\circ}C$ for 24 h. The resultant polymer forms several kinds of structures with different combination of initiators. The sole MeOTf initiator caused chain transfer reaction to form the one-order structure for which the resultant polymer exclusively formed pendant structure, while alkyl halide and MeOTf formed two kinds of structures, pendant and main chain, which is caused by partly-proceeded double isomerization polymerization by highly reactive nucleophilic counter anion of halogen. Merrifield polymer was also utilized as an intiator and copolymerized with TAO, which produced a graft structure.

Twisted Intramoecular Charge-Transfer Behavior of a Pre-Twisted Molecule, 4-Biphenylcarboxylate Bonded to Poly(Methyl Methacrylate)

  • 강성관;안교덕;조대원;윤민중
    • Bulletin of the Korean Chemical Society
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    • v.16 no.10
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    • pp.972-976
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    • 1995
  • A trace amount of 4-biphenylcarboxylate having a pre-twisted biphenyl moiety was attached to a poly(methyl methacrylate) side chain and the fluorescence properties of the chromophore were investigated in various solvents such as ethyl acetate and butyl chloride. At room temperature, the polymer exhibited a distinct red shift of the short wavelength emission (325 nm) and an enhanced emission intensity around 430 nm upon excitation at the absorption red edge. The temperature dependence of the intensity ratio (R) of the 325 nm emission to the 430 nm emission was observed when exciting at the red edge over the temperature range between -20 and 60 ℃. However, the temperature dependence was not observed when exciting at the shorter wavelength. The Arrhenius plot of the R value shows the activation energy of 6.0 kJ/mol which is in good agreement with the energy required for the twist of the biphenyl moiety. Together with the results of red edge excitation effects it was concluded that the pre-twisted geometry of the biphenyl moiety is preserved by the restriction of the polymer chain to facilitate the formation of the twisted intramolecular charge transfer (TICT) state upon excitation.

From the synthesis of functional RAFT agents to the design of functional latex particles

  • Bathfield M.;D'Agosto F.;Spitz R.;Charreyre M.T.;Delair T.;Dos Santos A.M.
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.319-319
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    • 2006
  • RAFT polymerization can produce under controlled conditions polymer chains incorporating well-defined chain ends. By designing a simple way of producing functional RAFT agents, a variety of ${\Box}-end$ groups was successfully introduced onto hydrophilic polymer chains. The ${\Box}-end$ group being a thiocarbonyl thio function was used as efficient chain transfer agent in dispersion or emulsion polymerization to produce original functional latex particles.

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Synthesis of High Molecular Weight Poly(Hexafluoropropylene Oxide) by Anionic Polymerization (음이온 중합에 의한 고분자량 헥사플루오르프로필렌 옥사이드 중합제의 합성)

  • Lee, Sang-Goo;Ha, Jong-Wook;Park, In-Jun;Lee, Soo-Bok;Lee, Jong-Dae
    • Polymer(Korea)
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    • v.32 no.4
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    • pp.385-389
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    • 2008
  • Chain propagation and chain transfer in anionic polymerization of hexafluoropropylene oxide were investigated under various reaction conditions such as the stabilization of reaction temperature, the amount of hexafluoropropylene solvent, and the feeding rate of hexafluoropropylene oxide monomer. Anionic initiator for the polymerization was synthesized from cesium fluoride and hexafluoropropylene oxide in tetraethyleneglycol dimethylether. It was possible to obtain a high molecular weight poly(HFPO) ($M_w$ 14800) using the anionic initiator in conditions of stabilized reaction temperature, and optimized addition of solvent and monomer feeding (HFP/initiator mole ratio=31.5 and HFPO feeding rate=11.67 g/hr). Otherwise, chain transfer reaction in anionic polymerization was increased. From the results of molecular weight in various reaction conditions, it was found that chain propagation and chain transfer in anionic polymerization of HFPO were very sensitive to reaction conditions.

Improvement of Efficiency in $\pi$-Conjugated Polymer Based on Phenothiazine by Introduction of Oxadiazole Pendant as a Side Chain

  • Choi, Ji-Young;Lee, Bong;Kim, Joo-Hyun;Lee, Kye-Hwan
    • Macromolecular Research
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    • v.17 no.5
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    • pp.319-324
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    • 2009
  • A new $\pi$-conjugated polymer, poly[(2-methoxy-(5-(2-(4-oxyphenyl)-5-phenyl-1,3,4-oxadiazole)-hexyloxy))-1,4-pheny1ene-1,2-etheny1ene-alt-(10-hexyl-3,7-phenothiazine )-1,2-ethenylene] (PTOXDPPV), was synthesized by the Heck coupling reaction. The electron transporting unit, conjugated 1,3,4-oxadiazo1e (OXD), is attached on the main chain via linear 1,6-hexamethylenedioxy chain. The band gap and photoluminescence (PL) maximum of PTOXDPPV are 2.35 eV and 565 nm, respectively. These values are very close to those of po1y[(2,5-didecyloxy-1,4-phenylene-1,2-etheny1ene )-alt-(l0-hexyl-3,7-phenothiazine)-1,2-ethenylene] (PTPPV), which does not have OXD pendant. The estimated HOMO energy level of PTOXDPPV was -4.98 eV, which is very close to that of PTPPV (-4.91 eV). The maximum wavelength of EL device based on PTOXDPPV and PTPPV appeared at 587 and 577 nm, respectively. In the PL and EL spectrum, the emission from OXD pendant was not observed. This indicates that the energy transfer from OXD pendants to main chain is occurred completely. The EL device based on PTOXD-PPV (ITO/PEDOT/PTOXDPPV/AI) has an efficiency of 0.033 cd/A, which is significantly higher than the device based on PTPPV (ITO/PEDOT/PTPPV/AI) ($4.28{\times}10^{-3}\;cd/A$). From the results, we confirm that the OXD pendants in PTOXDPPV facilitate hole-electron recombination processes in the emissive layer effectively.

A Novel Simulation Architecture of Configurational-Bias Gibbs Ensemble Monte Carlo for the Conformation of Polyelectrolytes Partitioned in Confined Spaces

  • Chun, Myung-Suk
    • Macromolecular Research
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    • v.11 no.5
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    • pp.393-397
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    • 2003
  • By applying a configurational-bias Gibbs ensemble Monte Carlo algorithm, priority simulation results regarding the conformation of non-dilute polyelectrolytes in solvents are obtained. Solutions of freely-jointed chains are considered, and a new method termed strandwise configurational-bias sampling is developed so as to effectively overcome a difficulty on the transfer of polymer chains. The structure factors of polyelectrolytes in the bulk as well as in the confined space are estimated with variations of the polymer charge density.