A new monomer, 2,3,6,7,10,11-hexa(methacrylate) triphenylene (HMTP), and its crystals have been successfully synthesized, and the solid-state polymerization under UV irradiation has been investigated. The photo polymerization of HMTP in solid was confirmed by the reduction of vinyl bonds in the FT-IR and UV spectra of PHMTP in comparison with the corresponding spectra of its precursor. Thus, IR spectroscope was used to follow the polymerization of HMTP crystals under UV irradiation, and kinetic studies show a first-order reaction with rate constant of 6.12 x 10(-3) min(-1). This value is slightly larger than that measured by the weight method. The polarizing optical microscope and X-ray diffraction were used to Study the crystal structure difference between the polymers and its monomer. The results show that the polymers' crystals obtained from photo polymerization kept the monomer crystal lattice. Because of strong overlap between the TT-electron of the triphenylene, the monomer and polymer crystals showed different fluorescence properties. All these results proved that the photo polymerization of HMTP crystals is governed by the packing structure of monomer molecules; in other words, this reaction is just lattice controlled polymerization. (c) 2005 Wiley Periodicals, Inc.