| Autor: |
Sirish K. Reddy, Harini Kilambi, Jeffrey W. Stansbury, Lauren Schneidewind, Christopher N. Bowman |
| Rok vydání: |
2009 |
| Předmět: |
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| Zdroj: |
Journal of Polymer Science Part A: Polymer Chemistry. 47:4859-4870 |
| ISSN: |
0887-624X |
| DOI: |
10.1002/pola.23503 |
| Popis: |
The impact of secondary functionalities on the radical-vinyl chemistry of monoacrylates characterized by secondary functionalities that dramatically enhance their polymerization rate was elucidated utilizing experimental and computational techniques. Firstly, bulk interactions affecting the acrylate reactivity towards photopolymerization were removed by polymerizing at 5 wt % monomer in 1,4-dioxane. Following deconvolution of bulk interactions impacting reactivity towards photopolymerization, a linear correlation between average polymerization rates and Michael addition reaction rate constants was observed on a logarithmic scale. This result indicates that the presence of the secondary functionality intramolecularly alters the monomer chemistry in a manner which impacts both of these distinct reaction types in a similar manner. These monomers exhibited reduced activation energies in both Michael addition and photopolymerization reactions as compared to hexyl acrylate. Reduction up to 20 ± 8 kJ mole -1 was observed for Michael addition reactions and 12 ± 1 kJ mole -1 for photopolymerization reactions, thereby explaining the higher reactivity of the acrylates characterized by the secondary functionalities. Cyclic voltammetry experiments conducted to investigate the nature of the acrylic double bonds indicated that the rapidly polymerizing acrylates are more readily reduced as compared to traditional acrylates. Further, a distinct monotonic correlation of the irreversible cathodic peak potentials of the (meth)acrylates to photopolymerization and Michael addition reactivity was observed. The computationally estimated acrylic LUMO energies characterized by the secondary functionalities (―2.3 eV to -2.*7 eV) were also found to be lower relative to hexyl acrylate (―2.2 eV). |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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