The polymerization of tert-butyl acrylate (tBA) was performed with triethylaluminum-(-)-sparteine, triethylaluminum-tertiary phosphine, triethylaluminum-n-BuLi and bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminium-t-BuLi complexes in toluene. The poly (tBA)s obtained with these initiators were rich in syndiotactic diad as observed by H-1 NMR analysis. On the basis of the triad and tetrad stereochemical information of the poly(tBA)s obtained using triethylaluminum-(-)-sparteine and triethylaluminum-n-BuLi, the polymerization reactions were found to obey Bernoullian statistics. Glass transition temperatures of the poly(tBA)s were measured by differential scanning calorimetry (DSC). A syndiotactic poly(tBA) (racemo (r) diad content: 65%) and an isotactic one (r = 19%) exhibited higher glass transition temperature (50 and 43 degrees C, respectively) than an atactic one (r = 50%, T-g = 21 degrees C). (C) 2000 Elsevier Science Ltd. All rights reserved.