Radical copolymerization of crotonyl compounds with styrene

Abstract

The monomer reactivity ratios for the radical copolymerization of crotononitrile (CN), methyl crotonate (MC), and n‐propenyl methyl ketone (PMK) with styrene (St) were measured at 60°C. in benzene and little penultimate unit effect was shown for these systems. The values obtained were: St–CN, r1 = 24.0, r2 = 0; St–MC, r1 = 26.0, r2 = 0.01; St–PMK, r1 = 13.7, r2 = 0.01. The rate of copolymerization and the viscosity of the copolymer decreased markedly as the molar fraction of the crotonyl compound in the monomer mixture increased. The Q–e values were also calculated to be as follows: CN, e = 1.13, Q = 0.009; MC, e = 0.36, Q = 0.015; PMK, e = 0.61, Q = 0.024. A linear relationship was obtained between the e values of the crotonyl compounds and their Hammett constants σm.

Reactive Surfactants in Heterophase Polymerization. 7. Emulsion Copolymerization Mechanism Involving Three Anionic Polymerizable Surfactants (Surfmers) with Styrene−Butyl Acrylate−Acrylic Acid

“…43 Methacrylates are usually more reactive than acrylates in reactions with styrene (for instance, r MMA ) 2.09 ( 0.3 and r methyl acrylate ) 0.22 ( 0.05 55 ). It seems also that the crotonate is reacting to some extent, although on the basis of the reactivity ratios of methyl crotonate with styrene one would expect hardly any copolymerization at all (r S ) 26, r methyl crotonate ) 0.01, at 60 °C in benzene 56 ). A similar fact was observed by Urquiola, who copolymerized styrene with the allylic surfmer TREM LF-40 (sodium dodecyl allyl sulfosuccinate) under similar conditions but at much higher monomer concentrations.…”

Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

“…The percentage of tin was calculated according to the Gilman and Rosenberg method [ 20 ], and subsequently the copolymer composition (f) was determined as shown in ( Table 4 ). The monomers reactivity ratios and the content of the reaction mixture and the copolymer was calculated according to the FR method [ 22 , 23 , 24 ] ( Table 5 ). The FR parameters for DBTM and ST ( Table 6 ) were calculated by plotting the relation between F(f-1)/f and F 2 /f.…”

Reactivity Ratios for Organotin Copolymer Systems

“…The monomer reactivity ratios and the content of the reaction mixture and the copolymer were calculated according to the R method [ 19 , 21 , 22 ] ( Table 4 ). Generally, from the values of the experimental reactivity ratios, tt is evident that r 1 ( k 11 /k 12 ) is negative so it will correct to zero [ 19 , 23 , 24 , 25 ].…”