Copolymerization of a polyhydrocarbon macromonomer with methyl acrylate and acrylonitrile in the presence of a lewis acid

Abstract

The free radical copolymerization of a vinyl-terminated hydrocarbon macromonomer, namely poly-1-butene with molecular weight 1,000, with methyl acrylate (MA) led to copolymers with broad molecular weight distributions, and even bimodal character. In the presence of alkylaluminum chloride Lewis acids, higher incorporation of MA was obtained. The polymer MW and mole% MA in the copolymer increase with their decreasing Lewis acid strength. The best result was obtained in the presence of 25 mole% Et,AICl versus MA at 60 "C which led to 82% of the polyhydrocarbon chains being derivatized and unimodal MW distribution. For the copolymerization of the polyhydrocarbon macromonomer and AN, the best results were obtained without Lewis acid in toluene using a free radical initiator at 125 "C.The model compound 2,2,4-trimethyl-l-pentene copolymerizes with both MA and AN in standard free radical conditions and the copolymerization parameters were determined.

Effect of Lewis Acids on Reactivity Ratios for (Meth)acrylate/Nonpolar Alkene Copolymerizations

“…To date, many Lewis acids have been used in radical copolymerizations; [1][2][3][4][5][6][7][8][9][10][11][12][13] however, quantitative data on their effect on monomer reactivity ratios is lacking. Herein, we describe the influence of Lewis acids on the monomer reactivity ratios for (meth) acrylates/nonpolar alkene copolymerizations.…”

A comparative study of swelling properties of hydrogels based on poly(acrylamide‐co‐methyl methacrylate) containing physical and chemical crosslinks

“…For cases of Fickian transport, the rate to approach to equilibrium can be characterized by diffusion coefficient value D, which can be calculated for planar geometry from the equation. 8,19…”

“…6 In monolithic delivery systems, the drug is initially dispersed or dissolved in the glassy polymer, and the solute release rate may be controlled by the polymer swelling rate and the velocity of the moving solvent front. 7,8 Sorption experiments are the simplest and commonest methods to investigate the diffusion characteristics. A glassy initially isotropic polymer sample becomes rubbery during solvent sorption and undergoes complex dimensional change for slab geometry.…”

Organic and polymer chemistry of electrophilic tri‐ and tetrasubstituted ethylenes

“…Zinc chloride also accelerated the copolymerization of acrylonitrile or methyl acrylate with 1,3‐dienes 102, 103. Catalysis with aluminum Lewis acids increased the reactivity of acrylonitrile or methyl acrylate, allowing copolymerization with a hydrocarbon macromonomer, but in this case the Lewis acid probably initiated not by enhancing the putative tetramethylene reactivity but instead through the oxidative decomposition of itself 104…”