Synthesis and photochemical reaction of novelp-alkylcalix[6]arene derivatives containing acryloyl or methacryloyl groups

Abstract

Novel polyfunctional (meth)acrylates with a calixarene backbone [calixarene (meth)acrylates] were synthesized in good yields by certain reactions of p‐methylcalix[6]arene (1a) or p‐tert‐butylcalix[6]arene (1b) with (meth)acrylate derivatives such as acryloyl chloride, methacryloyl chloride, (2‐methacryloxy)ethyl isocyanate, and glycidyl methacrylate. Polyfunctional acrylate 6a having poly(oxyethylene) spacer chain between 1a and acrylate groups was also synthesized by the reaction of the poly(oxyethylene) modified 1a with acrylic acid. Calixarene acrylate 6a was liquid at room temperature, although the other calixarene (meth)acrylates were solid at room temperature. The initial decomposition temperature (IDT) of the resulting calixarene (meth)acrylates was measured by the thermogravimetric analysis to evaluate the thermal stability, and it was found that some of the IDTs of the calixarene acrylates were over 400°C. This means that calixarene (meth)acrylates have very good thermal stability. The photopolymerization of the resulting some calixarene (meth)acrylates with (2‐phenyoxy)ethyl acrylate as a reactive diluent in the presence of photoinitiator proceeded smoothly upon irradiation with UV light. Therefore, polyfunctional (meth)acrylates with a calixarene backbone can be expected to be novel and thermally stable photoreactive acrylate oligomers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3071–3078, 1999

Methacrylated Calix[6]arenes as Low Shrinking Additives for Dental Restorative Composites

“…In this context, numerous tailor-made methacrylate cross-linkers, such as liquidcrystalline dimethacrylates, dendritic or hyperbranched methacrylates, methacrylated sol-gel-polycondensates, bismethacrylate macromonomers, and dimethacrylates containing bulky substituents, were evaluated as lowshrinking components for dental materials. [2] Calixarenes are a versatile class of macrocyclic compounds, which are easily formed by condensation, e.g., of ptert-butyl phenol with formaldehyde under formation of the cyclic tetra-, hexa-(so called calix [6]arene) or octamer in high yields. [3] Usually, calixarenes show relatively high melting points and a low solubility in common organic solvents.…”

“…[4] In this context, [6]arene was acylated with different carboxylic acid anhydrides to improve their solubility in dimethacrylate cross-linkers. An esterification of p-tert-butylcalix [6]arene 1 with octanoic anhydride followed by methacrylation of the residual hydroxy groups with methacrylic anhydride resulted mainly in the formation of a pentaoctanoatemonomethacrylate 2a. In the radical polymerization of methyl methacrylate the inhibition effect of residual hydroxy groups in 2a was evaluated.…”

“…The addition of 2a resulted in a significant decrease of the polymerization shrinkage, whereas the modulus of elasticity of the visible light cured composites was not affected. different polymerizable calix [4]-and calix [6]arene acrylates and methacrylates were synthesized as solid compounds showing a relatively high thermal stability. [5,6] Unfortunately, these derivatives exhibited only slight solubility in common dimethacrylates.…”

“…different polymerizable calix [4]-and calix [6]arene acrylates and methacrylates were synthesized as solid compounds showing a relatively high thermal stability. [5,6] Unfortunately, these derivatives exhibited only slight solubility in common dimethacrylates. The present paper describes methacrylated calix [6]arenes with improved solubility and their use as a low-shrinkage resin component for the visible light-curing of restorative composites.…”

“…[5,6] Unfortunately, these derivatives exhibited only slight solubility in common dimethacrylates. The present paper describes methacrylated calix [6]arenes with improved solubility and their use as a low-shrinkage resin component for the visible light-curing of restorative composites.…”