Preparation and characterization of three-dimensionally ordered macroporous syndiotactic poly(p-methylstyrene) Xu Zhang, Weidong Yan * , Haiqing Li, Xiaoli Shen Institute of Polymer Science and Engineering, Hebei University of Technology, Tianjin 300130, China Received 2 September 2005; accepted 3 October 2005 Available online 26 October 2005 Abstract Three-dimensionally ordered macroporous(3DOM) syndiotactic poly(p-methylstyrene) (sPPMS) with pore size 170 nm was fabricated by means of silica templates using (dbm) 2 Ti(OPh) 2 /MAO catalytic system. The resulting polymers were characterized by SEM, 13 C NMR, DSC and GPC. The results indicated that the 3DOM sPPMS were highly syndiotactic. GPC curves showed that the 3DOM sPPMS possessed lower Mn and broader MWD compared with bulk one. Meanwhile, DSC results revealed that three 3DOM sPPMS exhibited crystalline form II, and bulk sPPMS form III. q 2005 Elsevier Ltd. All rights reserved. Keywords: Dimensionally ordered macroporous polymer; Syndiotactic poly(p-methylstyrene); Coordination polymerization 1. Introduction Recently, there has been extensive interest in the creation of three-dimensionally ordered macroporous (3DOM) materials due to potential applications in photonic crystals, sensors, hierarchic battery electrodes [1–4]. A variety of 3DOM materials of varied composition, ranging from metals, inorganic oxides, semiconductors to polymers [5–8] have been fabricated by replicating colloidal crystal templates. In this method, the corresponding precursor solution infiltrates the interstitial voids of a crystal template and solidifies without disrupting the parent framework. A new porous materials with long-ranged periodic structure is then created by subsequently removing the template. An important feature of this method is that the resulting spherical voids originally occupied by the templates are highly ordered and interconnected via small channels. Up to now, As far as the preparation of 3DOM polymer is concerned, most previous studies have focused on the radical polymerization, crosslink by thermal treatment or exposure to UV light or X-radiation-initiated.[9–11] Instead of this, many 3DOM polymers have been fabricated by infiltrating colloidal crystals with solution of preformed polymers [12]. However, coordination polymerization which is sensitive to water and oxygen has been few reported. As is well known, polymer with high syndiotacticity exhibits excellent physical properties, such as high melting temperature, fast crystallization rate and low dielectric constant, as well as permeability resistance to gas. We have reported the investigation of 3DOM syndiotactic polystyrene [13]. And, it is known that postmodification of the polymer is an important method for creating novel materials with some special function. Therefore, choosing the syndiotactic polymer with functional group as matrix of 3DOM polymer is significant for further functionalizating 3DOM polymer and broading the scope of application of the 3DOM sPPMS. Therefore, in this communication, poly(p-methylstyrene) was used as candidate polymer by means of silica colloidal crystal template using b-diketonate titanium complex/methy- laluminoxane (MAO) to fabricate the 3DOM polymer with high stereoregularity. Thus, the resulting 3DOM polymers can be functionalized in benzyl groups. And it is expected that some advanced materials used as photonic materials and sensors can be created. 2. Experimental 2.1. Materials Ethanol, 25 wt% aqueous ammonia, 40 wt% hydrofluoric acid purchased from Tianjin Chemical Reagent Factory are of Polymer 46 (2005) 11958–11961 www.elsevier.com/locate/polymer 0032-3861/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.polymer.2005.10.013 * Corresponding author. Tel.: C86 22 26564866; fax: C86 22 26582421. E-mail address: yanwd@hebut.edu.cn (W. Yan).