Terpolymerization kinetics and properties of (tert-butylamino)ethyl methacrylate, alkyl methacralyte and styrene terpolymers

Abstract

Sa svrhom ispitivanja kopolimerizacijskih reaktivnosti provedene su terpolimerizacije tert-butilaminoetil-metakrilata (TBAEMA), oktadecil-metakrilata (ODMA) i metil-metakrilata (MMA) te TBAEMA, ODMA i stirena (St). Navedeni materijali potencijalno su primjenjivi kao reološki modifikatori u industriji maziva. Reakcije su provedene do niskih konverzija (< 10 mas. %) uz peroksidni inicijator pri temperaturi od 70 °C u dilatometru volumena oko 20 mL i uz ukupnu koncentraciju monomera u toluenu od 2 mol dm^-3. Na oba ternarna sustava ispitan je dizajn optimalnih eksperimenata prema kojemu je za potpuni opis terpolimerizacijskog sustava (međuovisnosti sastava smjese monomera i sastava terpolimera) dovoljno provesti samo tri eksperimenta pri čemu se udjeli monomera u pojedinoj reakcijskoj smjesi mijenjaju tako da jedan monomer ima udio 80 mol. %, a druga dva po 10 mol. %. Za predviđanje sastava polimera korišteni su omjeri kopolimerizacijskih reaktivnosti pripadajućih binarnih smjesa određeni u prijašnjim istraživanjima na Zavodu za tehnologiju nafte i petrokemiju Fakulteta kemijskog inženjerstva i tehnologije. Stvarni sastav sintetiziranih terpolimera određen je nuklearnom magnetskom rezonancijom (NMR). Toplinska stabilnost dobivenih terpolimera ispitana je termogravimetrijskom analizom.With the purpose of determining copolymerization reactivity ratios, terpolymerizations of 2-(tert-butylamino)ethyl methacrylate (TBAEMA), octadecyl methacrylate (ODMA), and methyl methacrylate (MMA) as well as that of TBAEMA, ODMA and styrene (St) have been conducted. The reactions were carried out with a peroxide initiator at 70 °C in a 20 mL dilatometer with total monomer concentration of 2 mol dm^-3 in toluene and terminated at low conversions (< 10 wt %). For both ternary systems the optimal experiment design was studied, according to which for a complete description of the terpolymer system (the interdependence of the composition of the monomer mixture and the composition of the terpolymer) only three experiments need to be performed, with alternating the monomer concentrations in each reaction mixture so that one monomer has a portion of 80 mol %, with the other two having 10 mol %. Copolymerization reactivity ratios of the corresponding binary mixtures were obtained from past research on Petroleum and Petrochemical Department, Faculty of Chemical Engineering and Technology, University of Zagreb, and used to predict the composition of terpolymers. Actual composition of synthesized terpolymers was determined from nuclear magnetic resonance (NMR) spectrums. Thermal stability of terpolymers was examined using thermogravimetric analysis (TGA)