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Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics

  • Yun Zhang
  • Hong Huang
  • Zhiling Liang
  • Houhe Liu
  • Ling Yi
  • Jinhong Zhang
  • Zhiqiang Zhang
  • Cheng Zhong
  • Yugang HuangEmail author
  • Guodong YeEmail author
Original Paper

Abstract

The free radical addition reaction is very important in UV curing. The benzoyl radical is the most commonly observed radical. In the addition process, the benzoyl radical adds to an acrylate monomer, forming a primary radical that has great value for subsequent research. In this article, a quantum chemical method was used to study the microscopic progression from the reactive complex to the saddle point. The reactions of three monomers (amylene, allyl methyl ether and methyl acrylate) with a benzoyl radical were evaluated in terms of geometry and energy. The results were also interpreted with an expanded version of the Polanyi rules and the interaction/deformation theory. The deformation energy of methyl acrylate was found to be the smallest, and the bond formation index showed that the transition state in the methyl acrylate system forms early, and can easily reach the saddle point. The activity of the monomer was ascertained by charge analysis and was further confirmed by the reaction rate. Mayer bond order curves depicted the constantly changing chemical bonds during formation and dissociation. Reduced density gradient analysis showed a weak interaction between the monomer and the benzoyl radical.

Keywords

Photopolymerization Radical addition Benzoyl radical 

Notes

Acknowledgments

This work is supported by the National Natural Science Foundation of China (Grant No. 21274032), the Natural Science Foundation of Guangdong Province (Grant No. 2014A030313500 and No. S2013040015594), the Scientific Research Program (Grant No. 1201431369) for Colleges and Universities under the direct supervision of the Guangzhou Education Bureau and the project of the high level university of Guangdong province.

Supplementary material

894_2017_3217_MOESM1_ESM.doc (90 kb)
ESM 1 (DOC 90 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Yun Zhang
    • 1
  • Hong Huang
    • 1
  • Zhiling Liang
    • 1
  • Houhe Liu
    • 1
  • Ling Yi
    • 1
  • Jinhong Zhang
    • 2
  • Zhiqiang Zhang
    • 3
  • Cheng Zhong
    • 4
  • Yugang Huang
    • 1
    Email author
  • Guodong Ye
    • 1
    Email author
  1. 1.Department of Chemistry, School of Pharmaceutical SciencesGuangzhou Medical UniversityGuangzhouPeople’s Republic of China
  2. 2.Department of Medical Genetics and Cell BiologyGuangzhou Medical UniversityGuangzhouPeople’s Republic of China
  3. 3.Department of Material and EngineeringZhengzhou University of Light IndustryZhengzhouPeople’s Republic of China
  4. 4.College of Chemistry and Molecular SciencesWuhan UniversityWuhanPeople’s Republic of China

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