Multi-Functional Poly(Vinylidene Fluoride) Graft Copolymers Atanu Kuila, Dhruba P. Chatterjee,* Nabasmita Maity, Arun K. Nandi Polymer Science Unit, Indian Association for the Cultivation of Science, Kolkata, 700032, India Correspondence to: A. K. Nandi (E-mail: psuakn@iacs.res.in) Received 18 April 2017; accepted 9 May 2017; published online 00 Month 2017 DOI: 10.1002/pola.28671 ABSTRACT: Poly(vinylidene fluoride) (PVDF) is known for its bio- compatibility, piezo and pyro-electricity, and membrane form- ing capability. In order to tune its properties, modification through grafting from approach by atom transfer radical poly- merization (ATRP) is preferred. Hydrophilic polymers like poly(ethylene glycol) methacrylate, poly(methacrylic acid), pol- y(dimethylaminoethyl methacrylate) (PDMAEMA), and so forth have been anchored from PVDF backbone in order to make permeation of water molecules through the PVDF based mem- branes. The successful solution grafting of PDMAEMA chains from PVDF backbone by ATRP resulted appreciable graft con- version and hence its bulk properties showed a significant change. This water soluble graft copolymer shows incredible mechanical and adhesive properties. PVDF-g-poly(n-butyl methacrylate) generates honey-comb porous film using “breath figure” technique. Recently, they have used further improvement of grafting where model ATRP initiators are anchored using atom transfer radical coupling and used them as macroinitiators for grafting. This approach simplified the grafting reactions even more and enabled successful grafting of a large number of monomers under relatively less drastic conditions with appreciable conversion compared with the pre- vious conditions. This technique has resulted interesting solu- tion properties, ion and electron conducting PVDF, antifouling membrane, super glue and super tough materials, capable of generating metal nanoparticles tunable with pH and tempera- ture. V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 00, 000–000 KEYWORDS: adhesive; ATRP; ATRC; conductivity; membrane; solubility INTRODUCTION Poly(vinylidene fluoride) (PVDF) has been a very useful commodity polymer due to its diversified applica- tions originating from significant pyro and piezo-electric prop- erties, 1 good biocompatibility, 2 and membrane forming ability. 3,4 However, different applications require modulation of these properties by union with other polymeric or non- polymeric materials. 3,5–12 In this respect, preparation of PVDF based blend or composite materials continued to be an accept- able approach. Now, given the limited solubility in many of the common, less hazardous solvents due to high degree of crystal- linity of PVDF, it is very much apparent that preparation of new PVDF based blends and composite materials with high level of interfacial contact between the components is rather difficult. An efficient strategy to overcome this problem is to covalently anchor other components on PVDF matrix which may increase compatibility with other useful polymers, so that a micro- or nano-phase separated composite with better inte- gration of properties result. Attempts to modify the properties of PVDF chain via copolymerization or forming block copoly- mers are also encouraging; however, that may affect the prop- erties of PVDF main chain. 13–15 Recently, grafting has emerged as a very widespread procedure for the synthesis of comb or brush like polymer. One can adjust the properties of the brush by changing the major grafting parameters like graft density, graft length, and chemical compo- sition. 16,17 Among the three grafting process, the major benefit of “grafting from” technique is that, the steric hindrance does not interfere the chain growth of the polymer. 18 Covalent graft- ing of polymer chains on PVDF backbone in a controlled fash- ion is a very much attractive strategy as it helps in retaining the properties of the parent polymer. However, in view of the very high bond dissociation energy of the (CAF) bond, 3 it is very dif- ficult to initiate the growth of polymer chains from the PVDF backbone. Grafting of polymers on PVDF backbone has been done mostly by free radical polymerization after generating free radical center on PVDF backbone via ozone treatment, per- oxide treatment or ionizing radiation. 19–22 However, these con- ventional radical polymerization techniques experience a lot of difficulty owing to the significant amount of homo polymeriza- tion, gel formation, backbone degradation, etc. 23 These undesired consequences triggered the use of con- trolled polymerization methods for the synthesis of PVDF *Present address of D. P. Chatterjee: Department of Chemistry, Presidency University, Kolkata, 700073, India V C 2017 Wiley Periodicals, Inc. WWW.MATERIALSVIEWS.COM JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2017, 00, 000–000 1 JOURNAL OF POLYMER SCIENCE WWW.POLYMERCHEMISTRY.ORG HIGHLIGHT