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Design and Preparation of Porous Polymers Dingcai Wu,*,† Fei Xu,† Bin Sun,† Ruowen Fu,† Hongkun He,‡ and Krzysztof Matyjaszewski*,‡ †Materials Science Institute, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, People's Republic of China ‡Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States CONTENTS 1. Introduction A 2. Direct Templating Methodology C 2.1. Direct Templating with Polymers as the Raw Material D 2.1.1. Infiltration D 2.1.2. Layer-by-Layer Assembly E 2.2. Direct Templating with Monomers as the Raw Material G 2.2.1. Conventional Polymerization H 2.2.2. Electrochemical Polymerization L 2.2.3. Controlled/Living Polymerization N 3. Block Copolymer Self-Assembly Methodology P 3.1. Self-Assembly with Block Copolymers as the Pore Template Q 3.2. Self-Assembly with Block Copolymers as the Source of the Framework S 3.2.1. Self-Assembly with Sacrificial Component S 3.2.2. Self-Assembly with Morphology Reconstruction W 3.2.3. Self-Assembly with Vesiculation X 4. Direct Synthesis Methodology Z 4.1. Microporous Polymers AC 4.1.1. Disordered Microporous Polymers AD 4.1.2. Ordered Microporous Polymers AG 4.2. Meso- and/or Macroporous Polymers AK 4.2.1. Radical Polymerization AK 4.2.2. Polycondensation AL 4.3. Hierarchical Porous Polymers AM 5. High Internal Phase Emulsion Polymerization Methodology AN 6. Interfacial Polymerization Methodology AO 7. Breath Figures Methodology AP 8. Other Methods AR 9. Summary and Perspective AR Author Information AT Corresponding Author AT Notes AT Biographies AT Acknowledgments AU Abbreviations AU References AV 1. INTRODUCTION Porosity can be viewed as a profound concept that helps us to understand nature and create advanced structures. There are some interesting examples in nature, such as hollow bamboo, honeycomb with hexagonal cells, and alveoli in the lungs (Figure 1a−c). Design and construction of porous architectures that mimic structures found in nature in synthesized materials, down to the micro- and nanoscale range, have long been an important science subject. Porous polymers (see some examples in Figure 1d−f) especially have received an increased level of research interest because of their potential to merge the properties of both porous materials and polymers. First of all, porous polymers can be designed to show the advantages of high surface area and well-defined porosity.1−3 Second, the porous polymers have easy processability. For example, they can be produced in a molded monolithic form4−7 or in thin films,8,9 which generates significant advantages in many practical applications. Moreover, some of them can even be dissolved in a solvent and then processed directly using solventbased techniques without destroying the porosity,10−12 which is almost impossible to imagine for other types of porous materials like activated carbons, zeolites, or porous silicas. Third, the diversity of synthetic routes for polymers facilitates the design and construction of numerous porous polymers capable of incorporating multiple chemical functionalities into the porous framework or at the pore surface.1,13−15 The functional porous polymers can be designed to demonstrate stimuli-responsive characteristics capable of reversibly changing the pore structure16−19 or even switching between the open and closed porous state after exposure to environmental stimulation.20,21 Such unique characteristics are generally unavailable in other porous materials. Last but not least, due to their organic nature, the polymeric frameworks are composed of light elements providing a weight advantage in many applications.22,23 Porous polymers can be used as gas storage and separation materials,5,13,22,28−46 as encapsulation agents for controlled release of drugs,47−51 as catalysts,52 as supports for catalysts53−56 and sensors,57,58 as precursors of nanostructured carbon materials,59−68 as supports for biomolecular immobili- Received: November 22, 2011 Review pubs.acs.org/CR © |

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