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Abstract
This experimental and theoretical study deals with the thermal spontaneous polymerization of n-butyl acrylate (n-BA). The polymerization was carried out in solution (n-heptane as the solvent) at 200 and 220 °C without adding any conventional initiators. It was studied with the five different n-BA/n-heptane volume ratios: 50/50, 70/30, 80/20, 90/10, and 100/0. Extensive experimental data presented here show significant monomer conversion at all temperatures and concentrations confirming the occurrence of the thermal self-initiation of the monomer. The order, frequency factor, and activation energy of the thermal self-initiation reaction of n-BA were estimated from n-BA conversion, using a macroscopic mechanistic model. The estimated reaction order agrees well with the order obtained via our quantum chemical calculations. Furthermore, the frequency factor and activation energy estimates agree well with the corresponding values that we already reported for bulk polymerization of n-BA.
Highlights
Free-radical polymerization has been initiated by a thermal initiator like ammonium persulfate [1]and azobisisobutyronitrile [2], or a method such as plasma [3], ultrasound [4], UV-irradiation [5], ionizing-irradiation [6], and redox initiation [7]
These results results agree with what one expects from free-radical polymerization; polymerization; that is, the conversion increases with time, monomer concentration, concentration, and and temperature
Addition, this this figure figure shows that the n-butyl acrylate (n-BA) self-initiation reaction in both solution and bulk media [39] is so strong that the monomer conversion can exceed 60% after only 220 min in the the absence absence of of any any external external initiators
Summary
Free-radical polymerization has been initiated by a thermal initiator like ammonium persulfate [1]. Low molecular weight acrylate resins synthesized through thermal monomer self-initiation polymerization can obviate the need for high amount of solvent. Thermally monomer-self-initiated polymerization is a good method for the synthesis of macromonomers as the occurrence of a β-Scission reaction, which is a prevalent reaction at high temperatures, leads to the formation of an unsaturated carbon double bond at the backbone of the produced shortened chain [29]. Such macromonomers have wide applications in the synthesis of brush polymers and graft copolymers [30].
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