Low conversion kinetics of terpolymerization of N,N‐dimethylaminoethyl methacrylate (DMAEM) and dodecyl methacrylate (DDMA) with methyl methacrylate (MMA) or styrene (ST) was investigated. Reactions were performed at 70°C, in toluene solutions, using peroxide initiator. The interdependence between terpolymer and monomer feed composition was successfully described by Alfrey‐Goldfinger equation and the unitary, binary, and ternary azeotropes were calculated. In MMA‐containing system, the wide pseudoazeotropic region with existence of true azeotropic point was observed and experimentally confirmed at the DMAEM:MMA:DDMA molar ratio of 56:41:3. In the ST‐containing system compositional heterogeneity was significant, more than 10 mol%. Required copolymerization reactivity ratios were determined by linear and nonlinear methods. The glass transition temperatures of synthesized terpolymers are found to be between those of the corresponding homopolymers and relative to their content. Increase in the MMA or ST contents and decrease in the DDMA content in terpolymers results in an increase in their glass transition temperatures. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers

No abstract

BACKGROUND: The properties of copolymers depend strongly on their composition; therefore in order to tailor some for specific applications, it is necessary to control their synthesis, and, in particular, to know the reactivity ratios of their constituent monomers. Free radical copolymerizations of N,N‐dimethylaminoethyl methacrylate (DMAEM) with styrene (ST) and methyl methacrylate (MMA) in toluene solution using 1‐di(tert‐butylperoxy)‐3,3,5‐trimethylcyclohexane as initiator at 70 °C were investigated. Monomer reactivity ratios were determined for low conversions using both linear and nonlinear methods. RESULTS: For the DMAEM/ST system the average values are r1 = 0.43 and r2 = 1.74; for the DMAEM/MMA system the average values are r1 = 0.85 and r2 = 0.86. The initial copolymerization rate, Rp, for DMAEM/ST sharply decreases as the content of ST in the monomer mixture increases up to 30 mol% and then attains a steady value. For the DMAEM/MMA copolymerization system the composition of the feed does not have a significant influence on Rp. The glass transition temperatures (Tg) of the copolymers were determined calorimetrically and calculated using Johnston's sequence length method. A linear dependence of Tg on copolymer composition for both systems is observed: Tg increases with increasing ST or MMA content. CONCLUSION: Copolymerization reactivity ratios enable the design of high‐conversion processes for the production of copolymers of well‐defined properties for particular applications, such as the improvement of rheological properties of lubricating mineral oils. Copyright © 2009 Society of Chemical Industry