Monomers for Adhesive Polymers, 4

Abstract

Hydrolytically stable, crosslinking bis(acrylamide)s 1a–1l or bis(methacrylamide)s 2a–2c were synthesized by reaction of acryloyl or methacryloyl chloride using primary or secondary amines. In addition, monomers 3a and 3b were obtained by amidation of 2,6‐dimethylene‐4‐oxaheptane‐1,7‐dicarboxylic acid (DMOHDA) with propylamine and diethylamine, respectively. The structures of the monomers were characterized by IR, 1H, and 13C NMR spectroscopy. All monomers containing N,N′‐monosubstituted carbamide groups were solids. Those containing N,N′‐disubstituted carbamide groups were water‐soluble liquids. Water‐soluble bis(acrylamide) 1d (N,N′‐diethyl‐1,3‐bis(acrylamido)propane) shows a radical polymerization reactivity in the presence of 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (AMPAHC) similar to that of glycerol dimethacrylate, as revealed by gelation experiments in water. 1d is hydrolytically stable in 20 wt.‐% phosphoric acid and can be used to substitute dimethacrylates in self‐etching dentin adhesives. Furthermore, this monomer was also suitable as a reactive diluent in composites.magnified image

Monomers for Adhesive Polymers, 5

“…On the other hand, the increasing residual unsaturation in copolymers formed in Table 5. Copolymerization of 1 with 3 (combination (iii)), [1] [19] It was evident that in the present system (iii), the polar phosphonic acid groups shield the second double bonds of the copolymerized difunctional monomer. The pendant double bonds, as well as the growing polymer radicals become less accessible to other propagating chain radicals.…”

“…[5] Monomers 2 and 3 (Scheme 2) were prepared as previously described. [1,3] Methyl methacrylate (MMA) was washed with a 5.0 wt.-% NaOH solution, dried over anhydrous sodium sulfate, and distilled from calcium hydride under argon. AIBN was purified by recrystallization from methanol.…”

“…In this respect, Summary: 2,4,6-Trimethylphenyl 2-[4-(dihydroxyphosphoryl)-2-oxa-butyl]acrylate (1) was synthesized by silylation of 2,4,6-trimethylphenyl 2-[4-(dimethoxyphosphoryl)-2-oxa-butyl]acrylate with trimethylsilyl bromide (TMSBr) and the hydrolysis of the silyl ester resulted in the formation of polymerizable phosphonic acid 1. The structure of this new monomer was characterized by IR, 1 H, 13 C and 31 P NMR spectroscopy. The monomer dissolves well in ethyl acetate, ethanol or water and shows a high hydrolytic stability.…”

“…new phosphonic acids [3,4] and bis(acrylamide)s, [1] which feature an enhanced hydrolytic stability, can be used to substitute commonly used methacrylates in self-etching enamel-dentin adhesives. Recently, we were able to synthesize new steric hindered a-methylsubstituted acrylate -containing dimethyl phosphonate groups.…”

Monomers for Adhesive Polymers, 7a

“…[6] In this context, new bis(acrylamide)s, for example, monomer 2, showed excellent solubility in water and organic solvents and both improved hydrolytic stability and biocompatibility compared to the currently used dimethacrylates. [7] In addition, it was found, [8] e.g., that both N-(2-hydroxyethyl)methacrylamide and monomer 1 demonstrate improved hydrolytic stability and very low cytotoxicity and therefore can be used to substitute the frequently used 2-hydroxyethyl methacrylate of current enamel-dentin adhesives.…”