Amphiphilic Polymer Co- networks Synthesis, Properties, Modelling and Applications 1 0 0 P F 9- 6 7 5 1 0 8 8 7 1 8 7 9 9/ 3 0 1 0. 1 oi: d g | or c. s s.r b u p s:// p htt n o 0 2 0 2 pril A 3 2 on d e h s bli u P View Online Polymer Chemistry Series Editor-in-chief: Ben Zhong Tang, TheHongKongUniversityofScienceandTechnology, HongKong,China 1 0 0 P F 9- Serieseditors: 6 57 Alaa S. Abd- El- Aziz, UniversityofPrinceEdwardIsland,Canada 1 80 Jianhua Dong, NationalNaturalScienceFoundationofChina,China 8 17 Jeremiah A. Johnson, MassachusettsInstituteofTechnology,USA 8 97 Toshio Masuda, ShanghaiUniversity,China 39/ Christoph Weder, UniversityofFribourg,Switzerland 0 1 0. 1 oi: Titlesintheseries: d g | 1: Renewable Resources for Functional Polymers and Biomaterials c.or 2: Molecular Design and Applications of Photofunctional Polymers and s s.r Materials b u 3: Functional Polymers for Nanomedicine p s:// 4: Fundamentals of Controlled/Living Radical Polymerization p htt 5: Healable Polymer Systems n o 6: Thiol- X Chemistries in Polymer and Materials Science 0 02 7: Natural Rubber Materials: Volume 1: Blends and IPNs 2 pril 8: Natural Rubber Materials: Volume 2: Composites and Nanocomposites A 9: Conjugated Polymers: A Practical Guide to Synthesis 3 on 2 10: Polymeric Materials with Antimicrobial Activity: From Synthesis to d Applications e sh 11: Phosphorus- based Polymers: From Synthesis to Applications ubli 12: Poly(lactic acid) Science and Technology: Processing, Properties, P Additives and Applications 13: Cationic Polymers in Regenerative Medicine 14: Electrospinning: Principles, Practice and Possibilities 15: Glycopolymer Code: Synthesis of Glycopolymers and their Applications 16: Hyperbranched Polymers: Macromolecules in- between Deterministic Linear Chains and Dendrimer Structures 17: Polymer Photovoltaics: Materials, Physics, and Device Engineering 18: Electrical Memory Materials and Devices 19: Nitroxide Mediated Polymerization: From Fundamentals to Applications in Materials Science View Online 20: Polymers for Personal Care Products and Cosmetics 21: Semiconducting Polymers: Controlled Synthesis and Microstructure 22: Bio- inspired Polymers 23: Fluorinated Polymers: Volume 1: Synthesis, Properties, Processing and Simulation 1 00 24: Fluorinated Polymers: Volume 2: Applications P 9-F 25: Miktoarm Star Polymers: From Basics of Branched Architecture to 76 Synthesis, Self- assembly and Applications 5 01 26: Mechanochemistry in Materials 8 78 27: Macromolecules Incorporating Transition Metals: Tackling Global 1 78 Challenges 9 9/ 28: Molecularly Imprinted Polymers for Analytical Chemistry Applications 3 0 1 29: Photopolymerisation Initiating Systems 0. oi:1 30: Click Polymerization g | d 31: Organic Catalysis for Polymerisation or 32: Synthetic Polymer Chemistry: Innovations and Outlook c. s 33: Amphiphilic Polymer Co- networks: Synthesis, Properties, Modelling s.r b and Applications u p s:// p htt n o 0 2 0 2 pril A 3 2 on d e h s bli u P Howtoobtainfuturetitlesonpublication: A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication. Forfurtherinformationpleasecontact: Book Sales Department, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, CB4 0WF, UK Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247 Email: [email protected] Visit our website at www.rsc.org/books View Online 1 0 0 P F 9- 6 7 5 1 0 8 8 7 1 8 97 9/ 3 0 1 0. 1 oi: d g | or c. s s.r b u p s:// p htt n o 0 2 0 2 pril A 3 2 on d e h s bli u P View Online Amphiphilic Polymer Co- networks 1 Synthesis, Properties, Modelling and 0 0 P F 9- Applications 6 7 5 1 0 8 8 7 1 8 7 9 9/ 03 Costas S. Patrickios 1 10. UniversityofCyprus,Cyprus doi: Email: [email protected] g | or c. s s.r b u p s:// p htt n o 0 2 0 2 pril A 3 2 on d e h s bli u P View Online 1 0 0 P F 9- 6 7 5 1 0 8 78 Polymer Chemistry Series No. 33 1 8 7 9/9 Print ISBN: 978-1 - 78801- 370- 3 03 PDF ISBN: 978- 1- 78801-5 76- 9 1 0. EPUB ISBN: 978- 1- 83916- 134- 6 1 oi: Print ISSN: 2044- 0790 d g | Electronic ISSN: 2044- 0804 or c. s A catalogue record for this book is available from the British Library s.r b u p © The Royal Society of Chemistry 2020 s:// p htt Allrightsreserved n o 20 Apartfromfairdealingforthepurposesofresearchfornon-commercialpurposesorfor 0 pril 2 pArcitv1a9te88staunddy,tchreitCicoispmyroigrhrteavinedwR,aelsapteedrmRiitgthedtsuRnedgeurlathtieonCso2p0yr0i3g,htth,iDsepsuigbnliscaatnidonPmataenyts A 3 notbereproduced,storedortransmitted,inanyformorbyanymeans,withouttheprior 2 on permissioninwritingofTheRoyalSocietyofChemistry,orinthecaseofreproductionin d accordancewiththetermsoflicencesissuedbytheCopyrightLicensingAgencyintheUK, e h s orinaccordancewiththetermsofthelicencesissuedbytheappropriateReproduction bli u RightsOrganizationoutsidetheUK.Enquiriesconcerningreproductionoutsidetheterms P statedhereshouldbesenttoTheRoyalSocietyofChemistryattheaddressprintedon thispage. Whilstthismaterialhasbeenproducedwithallduecare,TheRoyalSocietyof Chemistrycannotbeheldresponsibleorliableforitsaccuracyandcompleteness,nor foranyconsequencesarisingfromanyerrorsortheuseoftheinformationcontainedin thispublication.Thepublicationofadvertisementsdoesnotconstituteanyendorsement byTheRoyalSocietyofChemistryorAuthorsofanyproductsadvertised.Theviewsand opinionsadvancedbycontributorsdonotnecessarilyreflectthoseofTheRoyalSocietyof Chemistrywhichshallnotbeliableforanyresultinglossordamagearisingasaresultof relianceuponthismaterial. The Royal Society of Chemistry is a charity, registered in England and Wales, Number 207890, and a company incorporated in England by Royal Charter (Registered No. RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK, Telephone: +44 (0) 20 7437 8656. For further information see our web site at www.rsc.org Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK 7 0 0 P F Foreword 9- 6 7 5 1 0 8 8 7 1 8 7 9 9/ 3 0 A Brief Historical Note 1 0. 1 oi: The polymer science community will much appreciate Costas Patrickios's d g | efforts spending time and energy editing this book on amphiphilic or co- networks (APCNs). I for one am sure that this volume will teach me a c. s s.r great deal about this subject. b u I feel privileged having been asked to provide a foreword and thought that p s:// a brief personal note on the early history of APCNs, specifically, a few words p htt on how these materials became a significant subdiscipline in polymer sci- n o ence, would be of interest to workers in the field. 0 02 Interest in APCNs started to grow rapidly after it became clear that these 2 pril unique networks offer solutions for needs no other materials can satisfy. In A addition, research on APCNs is intellectually challenging particularly for sci- 3 on 2 entists engaged in the design and synthesis of novel polymers with unique d combinations of properties for the benefit of society. e sh For me, the road to APCNs led via the bioartificial pancreas. Very briefly: we ubli hypothesized that, in order to cure diabetes, we needed to implant into dia- P betic patients porcine (pig) insulin- producing β- cells protected against the human immune system (specifically, γ- immunoglobulin) by membranes that allow the simultaneous in-a nd- out permeation of glucose, insulin, oxygen and metabolic wastes, including carbon dioxide.1 Beyond these key require- ments, immunoprotecting membranes had to be biocompatible and bio- stable, had to have controllable pore sizes, be appropriately strong, elastic, processible, sterilisable, and, of course, reasonably priced. Our main objec- tive was to design a biologically suitable amphiphilic membrane transpar- ent to both hydrophilic (glucose, insulin) and hydrophobic (oxygen, carbon dioxide) molecules. Thus, our task was to synthesise a container, a ‘tea bag’, Polymer Chemistry Series No. 33 Amphiphilic Polymer Co- networks: Synthesis, Properties, Modelling and Applications Edited by Costas S. Patrickios © The Royal Society of Chemistry 2020 Published by the Royal Society of Chemistry, www.rsc.org vii View Online viii Foreword enveloping (immunoprotecting) a sufficient number of pancreatic β- cells by a thin membrane combining these key requirements. After years of experi- mentation, we perfected a functioning membrane consisting of covalently connected hydrophilic and hydrophobic domains, i.e., an APCN, that did the job. By implanting this device into a pancreatectomised dog, we were able to 7 00 keep it alive with our implanted artificial pancreas containing pig β- cells for P 9-F a couple of weeks.1,2 76 Over the course of these investigations, we learned a lot about APCNs and 5 01 our research led to many scientific articles and patents.3 Among other things, 8 78 we became aware of the fascinating and well- established field of contact 1 78 lens literature. It became clear to us that most extended-w ear contact lens 9 9/ researchers were, in fact, APCN researchers. Indeed, the vast contact lens 3 0 1 technology is a true fountainhead of APCN science and technology. 0. oi:1 In 2005, I felt the field of APCNs, particularly the intricacies of making g | d APCNs, needed a comprehensive critical review. Jointly, with one of my tal- or ented co-w orkers, Gabor Erdodi, we organised the scientific and patent liter- c. s ature of synthetic methodologies, and argued to adopt the terminology for bs.r APCNs first proposed by Iván. And we offered a definition of APCNs:4 u p s:// Amphiphilic co- networks are two- component networks of covalently intercon- p htt nected hydrophilic/hydrophobic (HI/HO) phases of co- continuous morphology; as n such they swell both in water and hydrocarbons, and respond to changes in the o 20 medium by morphological isomerisation (‘smart’ networks). 0 April 2 tecItnu trhe eo fc oAuPrCsNe so wf tahsi cs ownocrekiv, ewde j buestc aamboeu at wthaer es athmaet ttihme ed ienfi Gneinrmg maniyc raonadrc thhie- 23 U.S. Figure 1 reproduces the sketches published by Weber and Stadler5 and on Kennedy et al.6 some 30 years ago. It is quite apparent that the fundamen- d he tal message of these sketches, conceived an ocean apart, almost simultane- s bli ously, is in fact the same: APCNs are networks consisting of co- continuous u P Figure 1 APCN sketches by Weber and Stadler5 (left) and Kennedy et al.6 (right) drawn in 1988. Left reproduced from ref. 5 with permission from Elsevier, Copyright 1988. Right reproduced from ref. 6 with permission from Taylor and Francis, Copyright 1988. View Online Foreword ix hydrophilic–hydrophobic domains that allow the simultaneous permeation of hydrophilic and hydrophobic species. Most regrettably Stadler died not much after the publication of this semi- nal paper but research on APCNs was uninterruptedly continued in the U.S. Investigations during this early period were mainly driven by research and 7 00 development on extended-w ear contact lenses and the bioartificial pancreas. P 9-F Figure 2 was published during the turn of the century to help visualise 76 solvent mediated morphological isomerisation of APCNs, a defining feature 5 01 of these ‘smart’ materials.4 The cube in the centre of the figure depicts an 8 78 APCN in the dry state emphasising its bi- continuous morphology. The top 1 78 sketch shows swelling of an APCN immersed in a medium solubilising both 9 9/ the HI and HO network constituents. The sketches at the bottom of the fig- 3 0 1 ure show morphological changes (isomerisations) that occur when an APCN 0. oi:1 is immersed in a HI (water) or HO (hydrocarbon) solvent: depending on the d g | or c. s s.r b u p s:// p htt n o 0 2 0 2 pril A 3 2 on d e h s bli u P Figure 2 Sketches of the micromorphology of an APCN (centre), and changes caused by amphiphilic (common), HI, and HO solvents (morphological isomerisation, see text). Reproduced from ref. 4 with permission from Elsevier, Copyright 2006. View Online x Foreword philicity of the medium, one of the phases swells while the other stays col- lapsed. Importantly, co- continuity is preserved in either solvent and macro- scopic phase separation cannot occur due to the covalent bonds connecting the phases. These morphological changes are reversible (indicated by equi- librium signs). 7 00 Thus, APCNs are close relatives of hydrogels; in fact, these materials are P 9-F often called ‘siloxane hydrogels’ in the soft contact lens literature. 76 The individual chapters in this volume provide an excellent bird's eye view 5 01 of the present status of APCNs and hold clues as to the future of this science 8 78 and technology. 1 8 7 9 Joseph P. Kennedy 9/ 03 Polymer Science Department 1 0. The University of Akron, Ohio, USA 1 oi: [email protected] d g | or c. s.rs References b u s://p 1. G. Erdodi, J. Kang, B. Yalcin, M. Cakmak, K. S. Rosenthal, S. Grundfest- http Broniatowski and J. P. Kennedy, Biomed. Microdevices, 2009, 11, 297. n 2. S. F. Grundfest- Broniatowski, G. Tellioglu, K. S. Rosenthal, J. Kang, o 0 G. Erdodi, B. Yalcin, M. Cakmak, J. Drazba, A. Bennett, L. Lu and J. P. 2 0 2 Kennedy, ASAIO J., 2009, 55, 400–405. pril 3. See P. Kurian, B. Kashiblata, J. Daum, C. A. Burns, M. Moosa, K. S. A 3 Rosenthal and J. P. Kennedy, Part XXI of the series “Amphiphilic Networks”, 2 on Biomaterials, 2003, 24, 3493–3503, and earlier publications in this series. d e 4. G. Erdodi and J. P. Kennedy, Prog. Polym. Sci., 2006, 31, 1–18. h s bli 5. M. Weber and R. Stadler, Polymer, 1988, 29, 1064–1070. u P 6. D. Chen, J. P. Kennedy and A. J. Allen, J. Macromol. Sci., Chem., 1988, A25, 389–401.