Resumo

DE LAS HERAS, Myriam Gregorio et al. Nitroxide mediated polymerization of n-butyl acrylate using accelerating agents. Rev. Téc. Ing. Univ. Zulia [online]. 2007, vol.30, n.1, pp.96-108. ISSN 0254-0770.

Abstract The effect of the Dicumyl Peroxide (DCP), Acetol and Acetic Anhydride on the conversion evolution, and molecular weight distribution in bulk nitroxide mediated polymerizations of n-butyl acrylate (BA) was studied. Temperature profile was 1 h at 90°C, and variable reaction times (between 2 and 32 hours) at 135°C. Benzoyl peroxide (BPO) and 4-hidroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl (4-OH-TEMPO) were used as initiator and stable radical, respectively. Thermal, conventional, and nitroxide mediated polymerizations of the acrylic monomer were carried out for comparison purposes. Conversion was determined gravimetrically and some samples were selected for characterization by size exclusion chromatography (SEC). With DCP conversions were low and the polymerization was uncontrolled. Polymerization was inhibited for molar relation [DCP]/[4-OH-TEMPO] below of 0,5; independently of the [4-OH TEMPO]/[BPO]. With acetol, reaction rate increased respect to the polymerization without this agent. Conversions reached 66%, while the products showed relatively narrow molecular weight distributions (PD 1,35-2,01). The polymerization rate increased significantly at [Anh Ac]/[4-OH-TEMPO] ³ 4. In these cases, conversions were higher than 70% at first 2 h of reaction time. However, there was no control over these polymerizations. From the comparison of the effect for the studied agents, is possible to conclude that acetol produce better results on distribution of molar mass control, at acceptable polymer yields

Palavras-chave : Nitroxide mediated polymerization; 4-OH-TEMPO; n-butyl acrylate; accelerating agents.