Controlled Synthesis of Anisotropic Polymer Particles Templated by

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Controlled Synthesis of Anisotropic Polymer Particles Templated by Porous Coordination Polymers Takashi Uemura, Tetsuya Kaseda, and Susumu Kitagawa Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/cm4025843 • Publication Date (Web): 23 Aug 2013 Downloaded from http://pubs.acs.org on August 27, 2013

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Chemistry of Materials

Controlled Synthesis of Anisotropic Polymer Particles Templated by Porous Coordination Polymers Takashi Uemura,*,† Tetsuya Kaseda,† and Susumu Kitagawa*,†,§ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan and Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan. E-mail: [email protected], [email protected] †Department of Synthetic Chemistry and Biological Chemistry, Kyoto University § WPI-iCeMS, Kyoto University

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ABSTRACT. Non-spherical polymer particles have been efficiently prepared in different morphological crystals of porous coordination polymers (PCPs) by in situ radical polymerization of styrene and methylmethacrylate, followed by removal of the host PCP frameworks in aqueous tetrasodium ethylenediaminetetraacetate (Na-EDTA) solution. In this replication process, the isolated vinyl polymer particles retained the size and morphologies of the original PCP particles, although the polymer chains were not stabilized by cross-linking. This morphological retention of vinyl polymers after the isolation from the PCP matrices was ensured by the rigidity and porosity of the polymers, which was confirmed by DSC and adsorption measurements. The unconventional assembly of polymer chains in the particles is of interest from the viewpoints of functional properties of the polymer particles.

Keywords: Non-spherical polymer particles, porous coordination polymer, template synthesis, radical polymerization


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Introduction Polymer particles have attracted great interest because they play pivotal roles in many scientific and industrial areas such as electronics, photonics, sensors, medicine, biotechnology, and environmental technology.1-4 General methods of preparation of polymer particles include emulsion polymerization, dispersion polymerization, suspension polymerization, and seeded polymerization, which can produce monodispersed spherical polymer particles with controllable sizes depending on the synthetic conditions.1-4 In contrast, there has been growing interest in studying the preparation of anisotropic polymer particles owing to the more complex and useful structures into which these particles can potentially assemble.5-9 These anisotropic particles have both theoretical significance and practical applications in the fields of photonic crystals, optoelectronics, and sensors, as well as providing a platform for new phenomena and materials.10-12 However, reports on the preparation of non-spherical polymer particles are fewer as compared with those of spherical particles because of the lack of an effective fabrication process. One of the most promising methods for producing anisotropic polymer particles is shape transcription from host materials to organic polymers, where many host materials have been utilized to produce their replica of polymer particles via the template process.13-16 These direct replica methods have produced many libraries of unique geometrical particles made of polymers. Porous coordination polymers (PCPs), comprised of metal ions and bridging organic ligands, have recently emerged as an important family of porous materials because of their unique structural and functional properties.17-21 PCPs have highly regular and designable nanopores that can be utilized for storage, separation, and catalysis.22-25 For example, PCPs can provide the suitable pores for polymerization of caged monomers to control the structures of resulting


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polymers.26-28 Thus, the PCP can be regarded as a good candidate for the production of anisotropic polymer particles, where polymerization and subsequent dissolution of PCP templates would leave polymer particles replicated from non-spherical pristine PCP crystals.29-32 Note that crystal size and morphology of PCPs can be finely tuned depending on the preparation conditions.33-36 In addition, after the formation of PCP-polymer composites, selective dissolution of the PCP matrices can be performed under mild conditions because of the non-covalent framework structures, which is advantageous for the rational synthesis of the replicated polymer particles. In this work, we prepared [Zn2(bdc)2(ted)]n (1; bdc = 1,4-benzenedicarboxylate, ted = triethylenediamine) with different crystal morphologies (1a; cube, 1b; rod, and 1c; hexagon) by changing the synthetic conditions.37,38

Radical polymerization of vinyl monomers such as

styrene (St) and methyl methacrylate (MMA) in the nanochannels of 1 was performed, and subsequent isolation of the resulting polymers by dissolution of the host matrices in tetrasodium ethylenediaminetetraacetate (Na-EDTA) solution efficiently provided non-spherical polymer particles corresponding to the host PCP crystals. In spite of linear polymerization without crosslinking, morphologies of the pristine PCP crystals were precisely maintained to give polymer replicas during the isolation process. The keys to the morphological maintenance of polymer particles are also studied.

Experimental Section


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Materials. All the reagents and chemicals used were obtained from commercial sources, unless otherwise noted. 2,2′-azobis(isobutyronitrile) (AIBN) was recrystallized from MeOH solution, and vinyl monomers (St and MMA) were purified by vacuum distillation prior to use. Synthesis of 1. A solution of ted (0.187g, 1.67 mmol) in N,N-dimethylformamide (DMF; 20 mL) was transferred into a mixture of Zn(NO3)2·9H2O (1.000 g, 3.36 mmol) and bdc (0.560, 3.37 mmol) in DMF (20 mL). The resultant mixture was stirred for 3 h at room temperature, and was filtered to remove white precipitates. The filtrate was heated at 100 °C for 2 days, left at room temperature for 3 weeks, and heated 100 °C for 3 h, which gave cubic (1a), rod-like (1b), and hexagonal (1c) crystals, respectively.37,38

Polymerization of vinyl monomers in 1.39,40 The dried host compound 1 (200 mg) was prepared by evacuation (< 0.1 kPa) at 130 °C for 1 day in a Pyrex reaction tube. Subsequently, 1 was immersed in a monomer (1 ml) with AIBN (6 mg) at room temperature for 0.5 h to incorporate the monomer and the radical initiator into the nanochannels. After excess monomer external to the host crystals was removed completely by evacuation (St: 0.2 kPa, MMA: 2.0 kPa) at room temperature for 0.5 h, the reaction tube was filled with nitrogen, and heated to 70 °C to perform the polymerization of St and MMA for 48 and 24h, respectively. To isolate the polymer inside the channels, the composite was stirred for 4 days in a 0.05 M aqueous solution (40 ml) of sodium ethylenediaminetetraacetate (Na-EDTA) for the complete dissolution of the frameworks of 1. The collected polymer was washed with water and dried under a reduced pressure at room temperature. Measurements. The X-ray powder diffraction (XRPD) data were collected using a Rigaku RINT 2000 Ultima diffractometer employing CuKα radiation.


The scanning electron

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microscopy (SEM) images were collected by using a Hitachi S-3000N SEM system operated at an accelerating voltage of 5 kV. Samples were placed on a conducting carbon tape attached by SEM grid, and then coated with platinum. The IR spectra were measured employing a Thermo Scientific Nicolet iS5. The 1H NMR spectra were obtained using a JEOL A-500 spectrometer operating at 500 MHz. The thermogravimetric analysis (TGA) was carried out from room temperature to 500 °C at a heating rate of 10 °C min-1 using a Rigaku Instrument Thermo plus TG 8120 in a nitrogen atmosphere. Differential scanning calorimetry (DSC) was carried out with Seiko Instruments DSC 6220 under N2 atmosphere and 10 K min-1 heating rate. The gel permeation chromatography (GPC) measurements on the resulting polymers were performed in CHCl3 at 40 °C on three linear-type polystyrene gel columns (Shodex K-805L) that were connected to a Jasco PU-980 precision pump, a Jasco RI-930 refractive index detector, and a Jasco UV-970 UV/vis detector set at 256 nm. The columns were calibrated against standard PSt or PMMA samples. The SEM-energy-dispersive X-ray (EDX) measurements were conducted by using a JEOL JED-2300 detector in a JEOL JSM-5600 at an accelerating voltage of 15 kV. The X-ray fluorescence spectroscopy was performed using Rigaku EDXL300. Adsorption isotherms of nitrogen at 77 K were measured with a Quantachrome Autosorb-1 volumetric adsorption instrument.

Nitrogen gas of high purity (99.9999%) was used.

Prior to the adsorption

measurements, the sample was treated under reduced pressure (< 10–2 Pa) at 300 K for 5 h.

Results and Discussion Morphology and size of the PCP crystals 1 can be finely controlled by simply changing the reaction conditions. For example, 1 with different crystal morphologies (1a; cube, 1b; rod,


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and 1c; hexagon) were obtained by changing the reaction time and temperature.37,38 Template synthesis of polymer particles using these PCP crystals was performed by the introduction of vinyl monomers into the PCP pores and subsequent polymerization, followed by the removal of the host PCP frameworks.39,40 The monomer St was introduced into the nanochannels of 1 by immersion of 1 in St at room temperature, and then excess St outside the host crystals was evacuated under reduced pressure to give the host-monomer adduct.

Polymerization of St

accommodated in 1 was performed by heating the adduct with AIBN at 70 °C for 48 h to provide polymer composites 1⊃PSt (where PSt is polystyrene). XRPD measurements of 1⊃PSt clearly showed that the original framework structures of 1 were retained during the polymerizations (Figure 2).

Obvious changes in the relative peak intensities were detected after the

polymerization of St in the channels because accommodation of guest molecules changed the electron density in the pores.39 In addition, morphology of the host particles in SEM images was completely the same before and after the polymerization, which showed that the polymerization proceeded only within the nanochannels (Figure 3). The resulting PSt was quantitatively isolated from 1⊃PSt by dissolution of the frameworks of 1 in an aqueous Na-EDTA solution. Formation of PSt with the molecular weight of tens of thousands was fully confirmed by IR, 1H NMR, GPC, and elemental analysis. XRD pattern of the PSt did not show undesirable additional peaks corresponding to the residues of host frameworks 1. In the TGA of the PSt product, complete degradation up to 500 °C also indicated pure PSt without any inorganic impurity (Figure 4). In fact, SEM-EDX analysis of the isolated PSt demonstrated the removal of 1a during the polymer recovery process. The amount of Zn in the PSt product was less than 0.5 wt. %, which was determined by X-ray fluorescence spectroscopy. The isolated PSt was completely soluble in a


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variety of organic solvents, such as THF, chloroform, and DMF, supporting the highly pure and linear chain form of the structure. Interestingly, SEM measurement of the resulting PSt showed that, despite the non-crosslinked structure, polymer objects formed shape replica of the mother PCP crystals (Figure 3). Cubic, rod-like, and hexagonal PSt particles were consistently obtained from 1a, 1b, and 1c, respectively. Not only PSt powder particles but also large PSt cubes with the size of 500 µm could be produced using the PCP templates. In addition to the PSt system, we performed the same experiments using MMA and successfully obtained anisotropic polymethylmethacrylate (PMMA) particles that were replicated from the host PCP crystals of 1 with different morphologies.

It is thus noteworthy that we could efficiently fabricate non-cubic polymer

particles using PCP crystals with a controlled morphology as templates. In this replication system, it is interesting that the final polymer particles retain the size and morphologies of the original PCP particles (Figure 3), although a large mass fraction based on PCP frameworks was removed by dissolving away, and the polymer chains were not stabilized by cross-linking. Previous studies have reported that one of the reasons for the morphological maintenance during the isolation process is the inherent rigidity of the daughter polymers whose glass transition temperatures (Tg) are much higher than room temperature.13-15 In fact, treatment of the obtained PSt particles above the Tg (105 °C) resulted in the collapse of the shape of the particles (Figure 5a). However, it should be noted that the PSt isolated from 1a was in the metastable state, as suggested by differential scanning calorimetry (DSC) measurement (Figure 6).13

During the heating process in the first DSC scan, a distinct

exothermic peak appeared prior to the glass transition probably because of the reorganization of


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PSt chain assembly into stable form. The second run of the sample gave only the glass transition behavior, indicating an irreversible conformational change of PSt above the Tg. Another crucial key to the morphological maintenance should be porosity in the interior of the polymer particles.13,41,42 To verify the porosity of the PSt particles, we performed N2 gas adsorption measurements on bulk-synthesized PSt and our PSt particles prepared from 1a at 77 K (Figure 7). During the pretreatment (activation) of the samples, careful control of activation temperature prior to the adsorption measurements was essential because treatment of the sample at higher temperature induced rearrangement of polymer chains, and caused them to be packed efficiently (Figure 7), which was suggested by SEM and DSC (Figure 5a and 6). In this measurement, the bulk-synthesized PSt did not adsorb N2, indicating no porosity in the structure (Figure 7). In contrast, the cubic PSt obtained from 1a, despite the linear structure, clearly showed the adsorption of N2 (Figure 7). Pore size distribution analysis using Barrett-JoynerHalenda (BJH) method43 revealed the existence of mesopores with the diameter of 8.0 nm in the PSt particles, which is consistent with the hysteresis behavior of N2 in the material. Formation of porous voids in the PSt particles should be caused by the removal of host PCP framework as well as unreacted monomers from the original composite. Thus, conversion of St monomers in 1 has a significant influence on the morphology of the isolated PSt.

In fact, we decreased the

conversion of St with decreasing the reaction time, and found that morphology of PSt isolated from 1a collapsed when the conversion of St was lower (< 50 %) (Figure 5b). This is because the polymer chains are too sparse to maintain the morphology of the host PCPs during the isolation process. Therefore, stiffness, porosity, and amounts of polymers are the key to the overall dimensional retention of the polymer particles in our system. The combined control over


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the particle morphology and porosity would give great potential for design of intelligent soft matters.

Conclusion This work has demonstrated a new strategy that can allow transformation of microparticles from PCPs into polymers with complete morphological maintenance, resulting in efficient production of anisotropic particles of vinyl polymers by design. This morphological retention of polymers after the isolation from 1 with various size and shape was ensured by the rigidity and porosity of the polymers. Observation of the porosity in the polymer particles freed from the matrix indicated a complex hierarchical inverse replica at the nanometric level and a direct replica at the micrometric level, which will find novel applications in the area of plastic matter. Since rational morphology control of polymer particles is currently important for the preparation of plastic matters with complex forms, we believe that our methodology shown here will contribute to the development of polymer synthesis for the formation of non-spherical particles that can be utilized as building blocks for unique photonic crystals, optoelectronics, and sensors in the future.

Acknowledgments. This work was supported by Izumi Science and Technology Foundation, a Grant-in-Aid for Young Scientist (A), and a Grant-in-Aid for Scientific Research on Innovative Area “New Polymeric Materials Based on Element-Blocks (No. 2401)” from the Ministry of Education, Culture, Sports, Science and Technology, Government of Japan. We thank Prof. Y. Chujo of Kyoto University for access to SEM-EDX apparatus.


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Supporting Information Available: IR, 1H NMR, SEM, and EDX data. This material is available free of charge via the Internet at http://pubs.acs.org.


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Figure 1. Schematic image for template synthesis of polymer particles using PCPs as host matrices.

Figure 2. XRPD patterns of 1a, 1a⊃PSt, and PSt isolated from 1a. The host framework was maintained during the polymerization of St, and amorphous PSt without host residues was recovered after the dissolution of 1a.


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Figure 3. SEM images of (a) 1a, (b) 1a⊃PSt, (c) PSt isolated from 1a, (d) 1b, (e) 1b⊃PSt, (f) PSt isolated from 1b, (g) 1c, (h) 1c⊃PSt, and (i) PSt isolated from 1c. The morphologies of the host crystals retained even after the removal of the host frameworks.


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Figure 4. TG profile of PSt isolated from 1a. Complete degradation up to 500 °C indicates that the isolated PSt was not contaminated with inorganic impurities.

Figure 5. SEM images of PSt prepared in 1a after the heat treatment at 130 °C (a) and prepared at low conversion of St in the nanochannels (b). Scale bars = 500 µm.


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Figure 6. DSC profiles of PSt isolated from 1a. In the first scan, a distinct exothermic peak was observed because of the reorganizatiom of PSt chains during the heating process, which disappeared in the second scan.


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Figure 7. (a) Nitrogen adsorption (filled circle) and desorption (open circle) isotherms at 77 K on bulk-prepared PSt (black) and PSt isolated from 1a before (red) and after (blue) the heat treatment at 130 °C. (b) Pore-size distribution of PSt prepared in 1a using BJH method, determined from the nitrogen adsorption profile of the porous PSt particles.


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Controlled Synthesis of Anisotropic Polymer Particles Templated by

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