The kinetics of the free radical terpolymerization of diethyl maleate (DEM) (M, ) with methyl methacrylate (MMA) (M2 ) and styrene (M3 ) was investigated at 60 O C with AIBN as initiator. The analysis of the dependence of the terpolymer composition on the feed composition was difficult due to the similar chemical and physical properties of diethyl maleate and methyl methacrylate and also by the low content of the former monomer in the terpolymers. Finally, the terpolymer composition could be determined by means of microanalyses of carbon and hydrogen content. The results of these determinations were confirmed by 13C NMR spectroscopy. The initiation rate constant of AIBN was studied at different feed compositions by means of the inhibition method. For the study of the over-all polymerization kinetics of this ternary system it was necessary to take into account the dependence of the termination rate on the feed composition. It was found that not only the viscosity of the solution, but also the properties of the polymer segment next to the radical site have to be considered. Containing only parameters and constants measured independently from terpolymerization, the kinetic equation obtained described satisfactorily the initial over-all rates.

No abstract

4-(Diallylamino)pyridine (DAAP) cyclopolymerizes with free radical initiators yielding a polymer whose monomer units are identical with 4-pyrrolidinopyridine (PPY), a very active nucleophilic catalyst. It has been found that the catalytic activity of this polymer is higher than that of PPY in all reactions studied to date. We have synthesized copolymers of DAAP with neutral (JV^V-dimethylacrylamide), cationic (dimethyidiallylammonium chloride), and anionic (acrylic acid) monomers.The reactivity ratios were obtained at 60 °C and show that DAAP active chain ends react with the comonomer faster than with DAAP monomer. All comonomers displayed the opposite behavior. 13C NMR spectra show evidence of both cis and trans isomers in the five-membered ring of the DAAP repeat units. The acid-base properties of the copolymers were investigated with UV spectroscopy and show increasing basicity of the pyridine groups (higher pKa) with increasing comonomer content in the copolymers of DAAP with lV,lV-dimethylacrylamide and acrylic acid.No apparent dependence of pKa on composition was observed for the copolymers with dimethyidiallylammonium chloride.

Copolymers of 4-(diallylamino)pyridine (DAAP) with neutral, anionic, and cationic monomers were investigated as catalysts for esterolysis and esterification reactions. The former were carried out with p-nitrophenyl caproate as substrate in water at 30 °C and pH values ranging from 7 to 9. The copolymers proved in many cases to be more effective than the homopolymer of DAAP, which in turn was more active than the very effective low molecular weight nucleophilic catalyst 4-pyrrolidinopyridine (PPY). The specific catalytic activity increased with growing isolation of the DAAP monomer units in agreement with reports for other polymeric esterolytic catalysts. Copolymers with dimethylacrylamide followed Michaelis-Mentenlike kinetics. The homopolymer of DAAP and the copolymers also catalyzed the esterification of linalool with acetic anhydride in toluene at 80 °C. The moderate increases in the esterification rates for polymeric catalysts were comparable to or somewhat less than that obtained with DMAP.

The kinetics of the free radical copolymerization of diethyl maleate (M1 ) with methyl methacrylate (M2) was studied in bulk at 60°C with azoisobutyronitrile (AIBN) as initiator. The reactivity ratios of the system were determined by means of H NMR spectroscopy. The obtained values show that diethyl maleate is not only unable to homopolymerize (rI2 = 0) but also displays a very low tendency to incorporate in the polymer chain (rZ1 = 370) under the present conditions. Molecular weight measurements showed that a normal, although very slow growth reaction involving diethyl maleate takes place. Therefore, chain transfer could be neglected in the kinetic analysis. The dependence of the initiation rate constant on the monomer feed was analysed by means of the inhibition method. An equation for describing the observed dependence of polymerization rate on feed composition was derived taking into account the influence of solution viscosity on the termination rate constant (diffusion theory). a) Part of Ph. D. Thesis.