Atom Transfer Radical Polymerization of Poly(2-methacryloyloxyethyl methacrylate)

Abstract

Template polymerization of poly(2-methacryloyloxyethyl methacrylate)s (number-average molecular weight: 3.47 × 104, an average number of vinyl group in molecule: 163.4) prepared from poly(2-hydroxyethyl methacrylate) was carried out by using a copper-mediated atom transfer radical polymerization (ATRP). When the concentration of poly(2-methacryloyloxyethyl methacrylate) was less than 0.31 wt %, the polymerization was limited in the molecule and proceeded in a living manner at 25 °C. An apparent polymerization rate, 5.0 × 10-5 s-1, which was very close to that of the copper-mediated ATRP in bulk, indicates that the vinyl groups were highly concentrated in the molecule. The intensity of ethyl group detected by 1H nuclear magnetic resonance spectroscopy drastically decreased by polymerization, the gel permeation chromatography peak shifted to lower molecular weight side, and the dependence of solution viscosity on share rate was increased. These suggested that the ladderlike molecule was formed by the template polymerization. Glass transition temperature of ladderlike molecule measured by differential scanning calorimetry was observed at 210 °C.

Template Polymerization of Multi‐Vinyl Monomer with Poly(2‐hydroxyethyl methacrylate) Backbone

“…PHMA1 was previously synthesized by copper-mediated ATRP with DBX/ Bpy/CuBr and analyzed elsewhere. [30] Conversion of HEMA was about 50 wt%. Number-average molecular weight [Mn ¼ 2:36 Â 10 4 ] and molecular weight distribution [Mw=Mn ¼ 1:52] were measured by GPC.…”

“…[25][26][27] Ladder-like macromolecule was expected by template polymerization with long chain templates. The template polymerization of poly(2-methacryloyloxyethyl methacrylate), multi-vinyl monomer [MVM] with poly-(2-hydroxyethyl methacrylate) [PHEMA] backbone, was carried out by conventional radical polymerization [24,28,29] and atom transfer radical polymerization [ATRP] [30] (Scheme 1). The solution viscosity of product showed strong shear dependence, the glass transition temperature, Tg, of products was higher than 200 8C, indicating the products were ladder-like.…”

“…Kinetic analysis indicated that the vinyl groups were highly concentrated around activated radical as well as bulk state, the apparent polymerization rate of template polymerization in dilute solution was very close to that in bulk. [30] However, there was no evidence that the polymerization proceeded along backbone. When the template is a linear polymer chain with soft sequence, the backbone forms globule.…”

Nucleobase Containing Synthetic Polymers: Advancing Biomimicry via Controlled Synthesis and Self-Assembly

“…Dual initiation, and the associated bidirectional propagation, rendered the site of initiation immaterial. 95 Further to initiation and termination processes, the mode of propagation also deserves serious consideration. We have discussed above whether a step-growth polymerization may be favored over a chain-growth mechanism.…”

Synthesis of syndiotactic poly(methacrylic acid) by free‐radical polymerization of the pseudo‐divinyl monomer formed with methacrylic acid and catechol

“…The broadening of peaks is a typical phenomenon for the formation of hydrogen bonding. 10,27 To clarify the stoichiometry of the complex of catechol and MAA, Job plot 28 was measured by using the peak of OH group at 8.2-8.6 ppm. Figure 3 shows the Job plot.…”