A Polyamine Macromonomer Having Controlled Molecular Weight—Synthesis and Mechanism—

Abstract

Polyamine macromonomer possessing a polymerizable vinyl group at the chain end was synthesized by lithium amide catalyzed anionic self-polyaddition reaction of N,N'-diethyl-N-(4-vinylphenethyl)ethylenediamine. To elucidate the reaction mechanism for the macromonomer synthesis, the quantitative analyses were carried out on this reaction using double-wavelength UV method as well as UV fourth order derivative spectra method. The number average-molecular weight of the macromonomer was also measured with these UV methods. From these studies, it was concluded that one to one complex consisting of > NH and > NLi played an important role in the successive addition reactions. When the ratio of [>NH] to [ > NLi] became smaller to approach unity, there occurred a break point at which the rate of the addition reaction decreased sharply. The number average molecular weight of the macromonomer at the point was expressed by a simple equation (cf eq 7). Thus, it was possible to control the molecular weight of the polyamine macromonomer by adjusting the relative concentrations of > NH to > NLi in the initial mixture for the polyaddition reaction.

Preparation and Characterization of the Micelle-Forming Polymeric Drug Indomethacin-lncorporated Polyfethylene oxide)-Poly(β-benzyl L-aspartate) Block Copolymer Micelles

“…32 For a quantitative determination of IMC from IMC/PEO-PBLA micelles, two wavelengths, such as 322 and 347 nm, the maximum and minimum of the differential coefficient on the absorption of IMC, at which the PEO-PBLA micelle group shows no absorbance irrespective of its concentration, were selected. The gel exclusion molecular weights of these columns are 300 000 based on a pullulan (polysaccharides) standard and 500 000 based on a protein standard, respectively.…”

Resolution of lymphocyte subpopulations derived from rat spleen by polyamine‐graft‐PHEMA copolymer

“…Polyamine-graft-PHEMA copolymer (HAx) was prepared by radical copolymerization of HEMA with polyamine macromonomer in ethanol at 45"C, using V-65 as an initiator [15]. Polyamine macromonomer, synthesized according to the previous reports [16,17], had a number average molecular weight of approximately 3200. Copolymer was recovered as a precipitate from a large excess of diethyl ether at room temperature, followed by thorough drying in uacuo.…”

Adsorbed serum protein mediated adhesion and growth behavior of bovine aortic endothelial cells on polyamine graft copolymer surfaces

“…Polymer .synthesi.s N,N'-Diethyl-N (4-vinylphenethyl)ethylenediamine (EDAS) was synthesized by anionic addition reaction of N,N'-diethylethylenediamine (DEDA) with 1,4-divinylbenzene (DVB) using butyllithium as a catalyst, and purified by distillation under reduced pressure (b.p. 79°C/0.015 mm Hg) [27]. Polyamine macromonomer was then synthesized by selfpolyaddition reaction of EDAS using lithium diisopropylamide in THF [27].…”

“…Polyamine macromonomer was then synthesized by selfpolyaddition reaction of EDAS using lithium diisopropylamide in THF [27]. The lower molecular weight fraction of polyamine macromonomer formed during the polyaddition reaction was extracted using N,N-dimethylformamide (DMF) three times, and then the solvent was evaporated completely under vacuum at room temperature [27]. The molecular weight of polyamine macromonomer was determined by 'H-NMR spectrum (Mn), UV (Mn) and GPC (MGpC) measurements.…”