Monomers for Adhesive Polymers, 7^a

Abstract

Homopolymerization and copolymerization of N‐(2‐hydroxyethylmethyl)acrylamide (1) with N,N′‐diethyl‐1,3‐bis(acrylamido)propane (2) have been studied in ethanol/water solvents or in bulk. The polymerization rate exponent depends on the polymerization temperature and increased from 0.99 at 50 °C to 1.21 at 75 °C. The initial polymerization rate dependence on temperature between 50 and 75 °C in Arrhenius coordinates was linear. However, the slope increased with an increase in monomer concentration. The overall activation energy Ea varied from 64 kJ · mol−1 at 0.5 mol · L−1 to 76 kJ · mol−1 at 2.0 mol · L−1 monomer concentration. In addition, the reaction order with respect to the initiator AIBN deviated from the standard free radical polymerization kinetics. The exponent 0.42 indicated a significant participation of primary radicals in termination reactions. The polymerization reaction order declined from ideality as well, and the Ea and polymerization enthalpy changed with the batch composition variation, which could be explained through monomer/monomer, monomer/solvent, or monomer/polymer complexation. The chain transfer to polymer was considered as an origin for the polymer network formation in monomer 1 homopolymerization if its concentration in the batch was 1 mol · L−1 or higher. The more intensive polymerization acceleration with the monomer dilution and the greater heat released reduction with decrease in the monomer 1 to 2 ratios were evidenced in copolymerization. Nevertheless, the deviations from conventional reaction kinetics were not as pronounced as with acrylic or methacrylic acid polymerizations.magnified image

Monomers for Adhesive Polymers, 14 Synthesis and Radical Polymerization of 4-[11-(Acryloyl-methyl-amino)-undecyloxy]-phthalic Acid and {10-[1,3-Bis(methacrylamido)-propoxy]-decyloxy}-phthalic Acid

“…We found a similar E a value (64 kJ mol À1 ) for the radical hompolymerization of N-(2-hydroxyethylmethyl)acrylamide in ethanol/water. [19] The presence of two polymerizable groups in monomer 2 could be confirmed by gel-formation experiments. For this purpose, the monomers (30.0 wt%) were dissolved in ethanol together with AIBN (1.0 wt%) as the initiator, and the homogenous mixtures were polymerized at 65 8C.…”

“…The determined E a of 66.2 kJ mol −1 is a slightly lower value than usually obtained for AIBN initiated vinyl monomer polymerizations (80–90 kJ mol −1 ). We found a similar E a value (64 kJ mol −1 ) for the radical hompolymerization of N ‐(2‐hydroxyethylmethyl)acrylamide in ethanol/water …”

New Diluents for Dental Composites

“…The characterization of the monomers was carried out by means of 1 H NMR, 13 C NMR, and IR spectroscopy. The spectral data are in agreement with the expected structures.…”

“…After addition of the amine was completed, no residual anhydride could be detected by IR spectroscopy and the work-up was done by washing with 2 N hydrochloric acid (0.75 L), 5% sodium hydroxide solution (1.00 L) and water (4 × 1.00 L). After stabilization of the organic layer with BHT H NMR (400 MHz, CDCl 3 ): 2 isomers (≈1:1), δ (ppm) = 1.95 (s, 6H, CH 3, MA ), 2.08 and 2.09 (2 s, 1.5H each, CH 3, Ac ), 4.23-4.43 (m, 4H, OCH 2 ), 5.36-5.42 (m, 1H, OCH), 5.61 and 6.13 (2 s, 2H each, CH 2 ) 13. C NMR (100 MHz, CDCl 3 ): 2 isomers (≈1:1) δ (ppm) = 18.15 and 18.17 (CH 3, MA ), 20.6 and 20.8 (CH 3, Ac ), 62.2, 62.4, and 62.5 (OCH 2 ), 69.0 and 69.3 (OCH), 126.2, 126.3, and 126.4 (C C H 2 ), 135.62, 135.65, and 135.68 ( C CH 2 ), 166.2 and 166.7 (C O MA ), 170.0 and 170.4 (C O Ac ).…”

Urethane Dimethacrylates with Carboxylic Groups as Potential Dental Monomers. Synthesis and Properties

“…[15][16][17][18] A viable alternative to acrylic systems are the urethane di(meth)acrylates with an aliphatic (UDMA) or partially aromatic (TMX-UDMA) core structure, proposed initially for reducing the high viscosity of BisGMA that allow a higher filler loading and finally, attaining of a high conversion in the resin composites. 9,11,[19][20][21][22] An area of monomers research that has received insufficient attention is the approach of urethane di(meth)acrylates chemically modified with carboxyl groups.…”