Synthesis and Characterization of Curable Methacrylate-Based Monomers Mousa Ghaemy, 1 Sara Bekhradnia 2 1 Chemistry Faculty, University of Mazandaran, Babolsar, Iran 2 Pharmaceutical Sciences Research Center, Mazandaran University of Medical Sciences, Sari, Iran Received 27 April 2009; accepted 13 December 2009 DOI 10.1002/app.31977 Published online 17 March 2010 in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: The synthesis of new methacrylate-based, cur- able macromonomers, 4,4 0 -bis[2-hydroxy-3-aminopropylme- thacrylate] diphenyl ether (BHAPE) and 4,4 0 -bis[2-hydroxy-3- aminopropylmethacrylate] diphenyl methane (BHAPM), is reported. BHAPE and BHAPM were prepared by the reaction of glycidyl methacrylate (GMA) with 4,4 0 -diaminodiphenyl ether and 4,4 0 -diaminodiphenyl methane, respectively. The progress of the reaction was monitored by thin-layer chroma- tography (TLC), and the structure of the monomers was char- acterized by Fourier transform infrared (FTIR) and 1 H-NMR spectroscopy. Thermal curing of the monomers was con- ducted in a differential scanning calorimeter (DSC) with per- oxide as the initiator. Thermal curing of the monomers showed the highest rate at 100  C with the activation energy value in the range 80–90 kJ distilled/mol. The water absorp- tion properties of the cured samples in water, acidic, and basic solutions were studied. V C 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117: 467–472, 2010 Key words: curing of polymers; differential scanning calorimetry (DSC); resins; synthesis INTRODUCTION Crosslinking monomers are synthesized to improve the mechanical and processing properties of the composite. Such composites demonstrate reduced water uptake and self-adhesion to substrates. Vinyl ester and unsaturated polyester resins typically used in making composites contain high concentrations of reactive diluents, such as styrene, to allow these res- ins to be molded. However, because of the volatili- zation of styrene, nonvolatile reactive diluents, such as methacrylate-based macromonomers, offer a large advantage over current reactive diluents. The mono- mer matrix systems of the composites, which are currently mostly based on a mixture of dimethacry- lates, have to fulfill a number of basic requirements as far as the reactivity, stability, or toxicity of the monomers used and the properties of the formed polymer network are concerned. Informative reviews on different monomer systems are available. 1 Multi- functional monomers of low polymerization shrink- age and high degree of conversion, such as methac- rylate- and acrylate-based monomers, act as crosslinking agents and, thus, crosslink the polymer chains as the film is cured, forming links between oligomer molecules and other molecules in the for- mulation. 2–5 Monomers of this type are able to cure very rapidly and provide low volatility, high reactiv- ity, and good flexibility. 6 It has also been shown that the presence of pendent hydroxyl groups in dime- thacrylate compounds, such as bisphenol A glycol dimethacrylate, enhances polymerization rates because it increases the viscosity of the system because of strong hydrogen bonding. 7 These poly- mers have acquired prime importance in various avenues of industrial applications, especially in areas such as pharmaceutical use for drug delivery, 8 pres- sure-sensitive adhesives, 9 dental composites, 10,11 superabsorbents, 12 industrial coatings, leather adhe- sives, and nonlinear optical materials. 13–15 The im- portant factor that affects the flexibility of the poly- mer chain is the distance between double bonds in the crosslinker structure. In addition, final conver- sions are often limited by vitrification and topologi- cal factors governing steric crowding, accessibility of reactive sites, and kinetic access to pendant double bonds. 16,17 These problems can be partially over- come by the incorporation of long, flexible spacers between the vinyl groups. 18 In this article, we report the synthesis and charac- terization of two multifunctional methacrylate-based macromonomers with a long distance between func- tional groups. The monomers were prepared by a simple one-step reaction between GMA and aro- matic diamines, and the progress of the reactions was monitored by TLC. The final structure of the monomers was checked by 1 H-NMR and FTIR Correspondence to: M. Ghaemy (ghaemy@umz.ac.ir). Journal of Applied Polymer Science, Vol. 117, 467–472 (2010) V C 2010 Wiley Periodicals, Inc.