• Title/Summary/Keyword: Photoinitiated reaction

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Estimating Diffusion-Controlled Reaction Parameters in Photoinitiated Polymerization of Dimethacrylate Macromonomers

  • Choe, Youngson
    • Macromolecular Research
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    • v.11 no.5
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    • pp.311-316
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    • 2003
  • The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

Explorations of the Heteroatom Directed Photoarylation Reaction. A Review of the Photoinitiated Intramolecular Cycloaddition Reactions of Ylide Systems

  • Dittami, James P.
    • Journal of Photoscience
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    • v.10 no.1
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    • pp.21-35
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    • 2003
  • The photoinitiated intramolecular ylide-olefin addition has been developed as an approach for the construction of one ring and two chiral centers, two rings and three chiral centers or three rings and six chiral centers in a single experimental operation from relatively simple starting materials. These investigations have uncovered several interesting and unusual reactions, which are sensitive to controls such as wavelength, temperature and solvent.

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Renewable Monomer Based on Rosin in Photoinitiated Radical Polymerization

  • Shim, Sang-Yeon;Hong, Young-Taik
    • Journal of the Korean Applied Science and Technology
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    • v.17 no.3
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    • pp.192-197
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    • 2000
  • Rosin moeity-containing monomer was prepared by the reaction of abietic acid with 2-hydroxyethyl methacrylate in tetrahydrofuran(THF) using diethyl azodicarboxylate as a catalyst. This new monomer was photo-polymerized to give thin films in the presence of a radical type initiator. The rate of photo-polymerization and amount of cured polymer were determined using the residual yield method. A thermogravimetric analysis of the cured polymer showed that the film was stable up to 170oC, at which point the polymer film has lost 10 wt % of its weight.

Photopolymerization of Reactive Oligomers and Methacrylate/SBS Blends (반응성 올리고머 및 메타아크릴레이트/SBS 블렌드의 광중합)

  • 최영선;류봉기
    • Polymer(Korea)
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    • v.27 no.5
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    • pp.421-428
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    • 2003
  • The kinetics of photoinitiated polymerization of reactive oligomer methacrylates and oligomer methacrylate/SBS blends have been studied to characterize the diffusion-controlled reaction using Fourier Transform Infrared Spectroscopy-Attenuated Total Reflectance (ATR-FTIR). The polymerization rates of reactive oligomer methacrylates and oligomer methacrylate/SBS blends were autocatalytic in nature at the initial stage and then a retardation of the reaction conversion occurred gradually as the polymer matrix became vitrified, and finally the reaction became diffusion controlled. Photopolymerization behavior of methacrylate/SBS blends was well predicted using the diffusion-controlled reaction model. N-Vinyl-2-pyrrolidinone (NVP) as a reactive solvent was used to incorporate SBS into methacrylate to form semi-IPN via photopolymerization. Due to the high reactivity of NVP, polymerization rate increased with the increase of NVP content. As the content of NVP-SBS in the blends increased up to 10 phr, the reaction conversion maintained almost constant. But above 20 phr of NVP-SBS in the blends, the reaction conversion gradually decreased since the increase of viscosity affected on the photopolymerization rate. The semi-IPN films of methacrylate/SBS blends were transparent at room temperature as well as at increased temperature and were able to be applied to surface coating.