New Monomer Based on Eugenol Methacrylate, Synthesis, Polymerization and Copolymerization with Methyl Methacrylate–Characterization and Thermal Properties

Abstract

Poly(eugenyl-2-hydroxypropyl methacrylate) (PEUGMA), poly(methyl methacrylate) (PMMA) and poly(eugenyl-2-hydroxypropyl methacrylate-co-methyl methacrylate) (PEUGMA-co-MMA) were synthesized by a free radical polymerization route in the presence of azobisisobutyronitrile. EUGMA was synthesized by etherification of the eugenol phenolic hydroxyl group with glycidyl methacrylate. Polymers and copolymers were characterized using size exclusion chromatography, Fourier transform infrared, and nuclear magnetic resonance. The effects of the encumbering substituent on the thermal behavior of the polymers and copolymers were studied by differential scanning calorimetry, thermogravimetry (TG) and direct analysis, using real-time, time-of-flight mass spectroscopy (DART-ToF-MS) methods. The results obtained revealed that for PEUGMA, the average molecular weight was 1.08 × 105, and increased slowly with the decrease in the EUGMA content in the copolymer. The order of the distribution of dyads comonomer units in the copolymer chains estimated by the Igarashi method based on the reactivity ratio does reveal a random distribution with a tendency toward alternation. The glass transition temperature of PEUGMA (46 °C) increased with the MMA content in the copolymer, and those of the copolymer fit well with the Johnston’s linearized expression. The TG analysis of pure PEUGMA revealed a significantly high thermal stability compared to that of PMMA. During its degradation, the preliminary decomposition was at 340 °C, and decreased as the MMA units increased in the copolymer. The DART-ToF-MS analysis revealed that the isothermal decomposition of PEUGMA led to a regeneration of raw materials such as EUGMA, GMA and EUG, in which the maximum amount was achieved at 450 °C.

Microstructural, Thermal and Electrical Properties of Methyl Methacrylate and 1‐Hexene Copolymers Made by Dinuclear Ni‐Based Catalysts

“…In the presence of nitrogen, thermal degradation of PMMA demonstrated two steps of weight loss during thermal decomposition that is in agreement with the literature [75,76] . The first weight loss localized in the range of 155–275 °C that may be due to scissions of head‐to‐head linkages [76,77] . The second weight loss was observed in the 290–365 °C associated with scissions at unsaturated ends and random scission within the polymer chain [77,78] .…”

“…The first weight loss localized in the range of 155–275 °C that may be due to scissions of head‐to‐head linkages [76,77] . The second weight loss was observed in the 290–365 °C associated with scissions at unsaturated ends and random scission within the polymer chain [77,78] . The gas product included CO, CO 2 , CH 4 and other hydrocarbons.…”

A Low-Viscosity BisGMA Derivative for Resin Composites: Synthesis, Characterization, and Evaluation of Its Rheological Properties

“…The supernatant was collected (by decantation process), and the solvent was removed in the rotary evaporator. The crude product was purified through a flash column chromatography (FCC) using silica gel (60 mesh) as a stationary phase and an EA/ n -H elution system (4:6 by volume; mobile phase) [ 21 ]. Fractions collected from FCC indicated the presence of two dominant components: one was previously identified as dCl-BisGMA [ 12 ], and the other with relatively high polarity was further identified as the mCl-BisGMA (thin-layer chromatography (TLC, 0.1 mm thick silica gel coated aluminum plate) retention factor, RF = 0.81 and 0.47 of di- and mono-Cl-BisGMA, respectively).…”

Viscosity, Degree of Polymerization, Water Uptake, and Water Solubility Studies on Experimental Dichloro-BisGMA-Based Dental Composites

“…In this context, various derivatives of BisGMA have been synthesized by different researchers, in which the OH functional groups were partially or fully replaced with targeted substituents, including alkyls, aryls, ethers, and esters with small or bulky groups [3,[5][6][7][8][9][10][11][12]. Regardless of the type of substituent used, the viscosity of BisGMA was greatly reduced after modification, confirming that H-bonding is the major cause of its high viscosity character [2,6,10,12,13]. Adversely, substitution may affect the hygroscopic, mechanical, DC, and some other critical physicochemical properties of the composites.…”