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Library of Congress Cataloging-in-Publication Data
ISBN 978-1-119-59202-0
The scientific literature with respect to functional synthetic polymers is collected in this monograph. The text focuses on the basic issues and also the literature of the past decades. The book provides a broad overview of the synthesis procedures for functional synthetic polymers and the materials used therein.
In addition to basic issues concerning functionalized polymers, particular emphasis is given to the principles of functionalization, basic functional groups, and surface functionalization. Also, fields of special application, such as electrical applications, water cleaning methods, and medical and pharmaceutical applications, are reviewed.
Beyond educating students of polymer chemistry, this book will be of importance to chemists and other scientists in specialty fields, such as electronics, medicine and pharmacology, interested in expanding their knowledge about topics concerning the issues in this field.
Among the special issues addressed in the text are: Surface functionalization supramolecular polymers, shape-memory polymers, foldable polymers, functionalized biopolymers, supercapacitors, photovoltaics, lithography, cleaning methods, such as recovery of gold ions olefin/paraffin, separation by polymeric membranes, ultrafiltration membranes, and other related topics.
Utmost care has been taken to present reliable data. However, because of the vast variety of material presented herein, it is not possible to include detailed information on all aspects of the topic, and it is recommended that the reader study the original literature for more complete information.
There are three indices: an index of acronyms, an index of chemicals, and a general index. In the index of chemicals, compounds that occur extensively are not included at every occurrence, but rather when they appear in an important context. When a compound is found in a figure, the entry is marked in boldface letters in the chemical index.
I am indebted to our university librarians, Dr. Christian Hasenhüttl, Dr. Johann Delanoy, Gerlinde Iby, Franz Jurek, Margit Keshmiri, Friedrich Scheer, Christian Slamenik, Renate Tschabuschnig, and Elisabeth Groß for their support in literature acquisition. In addition, many thanks to the head of my department, Professor Wolfgang Kern, for his interest and permission to prepare this text.
I also want to express my gratitude to all the scientists who have carefully published their results concerning the topics dealt with herein. This book could not have been otherwise compiled.
Last, but not least, I want to thank the publisher, Martin Scrivener, for his abiding interest and help in the preparation of the text. In addition, my thanks go to Jean Markovic, who made the final copyedit with utmost care.
Leoben, 7th February 2019
In organic chemistry, functionality is often used as a synonym for a functional group. Functionalization means the introduction of functional groups. According to IUPAC (1), the functionality of a monomer is defined as the number of bonds that a repeating unit of a monomer forms in a polymer with other monomers. Thus, in the case of a functionality of f = 2, a linear polymer is formed by polymerizing a thermoplastic material.
Monomers with a functionality of > 3 lead to a branching point, which can result in crosslinked polymers, i.e., a thermosetting polymer (2).
Functional polymers are also sometimes called smart polymers (3). Here, the basic issues of functionalized polymers are discussed.
Functional polymers are polymers with advanced optic and/or electronic properties. The advantages of functional polymers include their low cost, the ease in which they can be processed and a range of attractive mechanical characteristics for functional organic molecules.
These properties can be adjusted whilst material usage is kept low, consequently opening interesting environmental perspectives. Polymer-bound substances can spread their activity without endangering people or the environment. Examples of functional polymers are (4):
Functional polymers are macromolecules to which chemically bound functional groups are attached which can be utilized as reagents, catalysts, protecting groups, and others. Functional polymers are low cost, easy to process and have a range of attractive mechanical characteristics for functional organic molecules.
The polymer support can be either a linear species, which is soluble, or a crosslinked species which is insoluble. A polymer that can be used as support should have significant mechanical stability under the reaction conditions. Such properties of the support play an important role in the functionalization reactions of polymers. So, the polymer properties can be modified either by chemical reactions on pendant groups or by changing the physical nature of the polymers. Special uses of functional polymers are shown in Table 1.1.
Table 1.1 Uses of functional polymers (5).
| Field of Application | Use |
| Analytical chemistry | Polymers as stationary-phase (chromatography/extraction) |
| Catalysis engineering | Polymers as a catalyst |
| Medicine, agriculture, washing agents | Controlled release from polymer matrices, design and synthesis of functional polymers, polymer-bound dyes, reactive and functional polymers |
| Polymer modification | Surface and functional coatings |
There are monographs dealing with functional polymers (6–14).
A comprehensive and authoritative overview of functional polymers and polymeric materials has been presented (14). This ranges from their synthesis and characterization, to their properties, actual applications and future perspectives.
Functional polymers and smart polymeric materials play a decisive role in new innovations in all areas where new materials are needed. Optoelectronics, catalysis, biomaterials, medicine, building materials, water treatment, coatings, and many more applications rely on functional polymers.
Functional polymers are polymers that respond to different stimuli or changes in the environment. The types of polymers, including temperature-, pH-, photo-, and enzyme-responsive polymers, have been assessed (10). These issues include shape-memory polymers, smart polymer hydrogels, and self-healing polymer systems.
Applications of functional polymers include smart instructive polymer substrates for tissue engineering, smart polymer nanocarriers for drug delivery, the use of smart polymers in medical devices for minimally invasive surgery, diagnosis, and other applications, and smart polymers for bioseparation and other biotechnology applications. Functional polymers are also used for textile and packaging applications, and for optical data storage.
Adaptive polymers are those which are responsive to different stimuli, namely physical, mechanical, chemical and biological stimuli, with a controlled and/or predicable behavior. They can be used in textiles, skin care, medicine and other related areas. Some versatile functional polymers, such as chitosan, cylodextrin and dendrimer, and hyperbranched polymers have also been reviewed (8).
Functional polymers are also important materials for coatings (11). For example, superhydrophobic surfaces can be produced.
Also, functional biopolymers have been reviewed (15). A comprehensive overview of the synthesis, properties and biomedical applications of functional biopolymers has been presented. A lot of topics are covered, such as synthetic biopolymers, blood-compatible polymers, ophthalmic polymers and stimuli-responsive polymers. An up-to-date review of cell encapsulation strategies and cell surface and tissue engineering has also been included in this work.
Actually, standards specifically designed for functional polymers are rare. No standard with the term functional polymer in the title could be found. However, in the scientific literature, in the context of functional polymers, some standards for measuring the properties of these polymers have been mentioned. These standards are collected in Table 1.2.
Table 1.2 Standards in the context of functional polymers.
| Number | Title | Reference |
| ASTM D3643-15 | Standard Test Method for Acid Number of Certain Alkali-Soluble Resins | (16) |
| ASTM D790-17 | Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials | (17) |
| ASTM D785-08 | Standard Test Method for Rockwell Hardness of Plastics and Electrical Insulating Materials | (18) |
| ASTM D638-14 | Standard Test Method for Tensile Properties of Plastics | (19) |
| ASTM D570-98 | Standard Test Method for Water Absorption of Plastics | (20) |
| ASTM F813-07 | Standard Practice for Direct Contact Cell Culture Evaluation of Materials for Medical Devices | (21) |
| ASTM F619-14 | Standard Practice for Extraction of Medical Plastics | (22) |
| ASTM D5229 | Standard Test Method for Moisture Absorption Properties and Equilibrium Conditioning of Polymer Matrix Composite Materials | (23) |
| ASTM D2872-12e1 | Standard Test Method for Effect of Heat and Air on a Moving Film of Asphalt (Rolling Thin-Film Oven Test) | (24) |
| ISO 17736 | Workplace air quality – Determination of isocyanate in air using a double-filter sampling device and analysis by high pressure liquid chromatography | (25) |
| ISO 8986-1 | Plastics – Polybutene-1 (PB-1) moulding and extrusion materials – Part 1: Designation system and basis for specifications | (26) |
The Functional Polymers Group of the National Institute of Standards and Technology in Gaithersburg, MD, develops directives, measurement methods, data, standards, and science for the functional properties (e.g., electronic, ion transport) of polymeric materials within functional devices and applications in forms that include thin films, interfaces, nanostructures, and membranes (27). The projects and programs of this group are summarized in the following sections.
Here, measurements were developed and applied with high-spatial and chemically specific resolution to elucidate the properties and process kinetics of critical materials at nanometer scales that are needed to advance next-generation photolithography, including both the 193 nm (deep ultraviolet) and 13.5 nm (extreme ultraviolet) lithography platforms.
This provides the foundation for a rational design of materials and processing strategies for the fabrication of sub-32 nm structures. The measurement platform integrates specular and off-specular X-ray and neutron reflectivity, near-edge X-ray absorption fine structure spectroscopy, quartz crystal microbalance, solid-state nuclear magnetic resonance, polarization-modulation infrared reflectance absorption spectroscopy, and infrared variable angle spectroscopic ellipsometry. These measurements relate the fundamentals of polymer interfaces to high-resolution lithographic patterning.
Block copolymers are materials that naturally self-assemble into monodisperse, chemically distinct domains, however, their placement and orientation are difficult to control. Recent work has demonstrated a capability to utilize these domains as masks for pattern transfer and as functional materials for membranes.
Viable nanomanufacturing of templated block copolymers will require a capability to control the orientation and the line edge roughness of trillions of structures to within a single nanometer. However, there are no existing platforms that meet this need. Small-angle X-ray and neutron scattering techniques were developed to measure the orientation, orientation distribution, and pattern quality of block copolymers ordered on chemical and physical templates over large areas with high precision.
These parameters are the key to developing effective nanomanufacturing strategies. A methodology was developed to create large area block copolymer films with a highly preferred orientation. These samples are then suitable for characterization by small-angle scattering to determine an orientation distribution indicative of pattern quality, including line edge roughness.
This capability provides powerful data on the relationship between materials, processing, template design, and the expected pattern quality.
The objective of this project is the development of tools to measure the fundamental structure-processing and structure-property relations associated with sustainable polymer composites.
This will be accomplished by using interface characterization methods, such as Förster resonance energy transfer, nuclear magnetic resonance spectroscopy and Raman spectroscopy, to quantify the effects of the complex interactions and high degree of chemical functionality characteristic of the interface of these materials.
These methods will be coupled with mechanical property measurements to characterize the effect of mechanical degradation, aging, and hydrothermal effects on interface structure and integrity in sustainable/conventional composite blends and biobased polymer nanocomposites.
The structure and dynamics of important classes of polymer electrolyte membrane materials should be elucidated, including emerging systems like block copolymers, polymer blends, and candidate materials.
Advanced methods were developed that illuminate the relationship between the molecular architecture and the resulting nanostructure of a polymer electrolyte membrane material, information which is key to understanding the membrane performance, including durability and proton conductivity. The measurement methods should provide the precise 3D nanoscale morphological information that is missing from conventional analyses of these materials.
Small-angle neutron scattering techniques are developed that characterize the structure of hydrated, nanostructured membranes based on block copolymers and complex polymer blends.
In addition, quasielastic neutron scattering methods are tested for the analysis of polymer and water dynamics in both dry and hydrated membrane materials. Quasielastic neutron scattering was used to measure the correlations between counterion dynamics and bulk mechanical relaxations in alkyl ammonium neutralized membranes. These measurements have provided a physical description of how the network structure contributes to the ionic conductivity properties of the membrane.
Membranes and membrane technology are key to water and energy security. Polymer-based membranes already play a significant role in fields such as impact ballistic testing of polymer films.
The Membranes for Clean Water project provides measurement solutions that probe the surface and internal structure of polymer membranes used in water purification, and correlate that structure to the transport of water and other species through the membrane. The methods are focused on elucidating the role of roughness, surface charge, surface chemistry, crosslink density and monomer chemistry on the interfacial and internal dynamics of the membrane. With this knowledge, the industry will better understand the performance of these membrane materials, as well as identify essential features to enable next-generation, energy-efficient, high-flux membranes.
Polymer films and coatings play a central role in high impact mitigation applications ranging from helmets, to body armor, to aircraft and spacecraft.
Although there are very many energy dissipating mechanisms available for polymeric materials, the specific mechanism for high impact scenarios depends on the polymer structure and is not well understood.
Specifically, the mechanical testing infrastructure is developed in order to establish relationships between the polymer structure and physics that underpin the mechanical performance of engineered structures, composite interfaces, thin films and membranes. The investigated methods are laser-induced projectile impact testing, wrinkling-cracking, cavitation rheology, contact adhesion testing, poromechanical relaxation indentation, and neutron scattering.
Additionally, by coupling the results from these experimental measurements with theory, simulation, and modeling, the computational design of energy mitigating materials is facilitated.
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2. Wikipedia contributors, Functionality (chemistry) — Wikipedia, the free encyclopedia, https://en.wikipedia.org/w/index.php?title=Functionality_(chemistry)&oldid=804812838, 2017. [Online; accessed 27-October-2018].
3. Wikipedia contributors, Smart polymer—Wikipedia, the free encyclopedia, https://en.wikipedia.org/w/index.php?title=Smart_polymer&oldid=861339882, 2018. [Online; accessed 1-October-2018].
4. Wikipedia Contributors, Functional polymers — Wikipedia, the free encyclopedia, https://en.wikipedia.org/w/index.php?title=Functional_polymers&oldid=859144249, 2018. [Online; accessed 28-September-2018].
5. OMICS International, Functional polymer and its applications, electronic: https://www.omicsonline.org/conferences-list/functional-polymer-and-its-applications, 2018.
6. R. Arshady and A. Guyot, eds., Functional Polymer Colloids & Microparticles, Citus Reference Series, Citus, London, 2002.
7. M.R. Aguilar, C. Elvira, A. Gallardo, B. Vázquez, and J. Román, Smart polymers and their applications as biomaterials in N. Ashammakhi, R. Reis, and E. Chiellini, eds., Topics in Tissue Engineering, Vol. 3, chapter 6, pp. 1–27. Woodhead Publishing, an imprint of Elsevier Science, Sawston, UK, 2007.
8. J. Hu, Adaptive and Functional Polymers, Textiles and their Applications, Imperial College Press, London, 2011.
9. V. Mittal, ed., Functional Polymer Blends: Synthesis, Properties, and Performances, CRC Press, Boca Raton, 2012.
10. M. Aguilar and J. San Román, eds., Smart Polymers and their Applications, Woodhead Publishing, an imprint of Elsevier Science, Sawston, UK, 2014.
11. L. Wu and J. Baghdachi, eds., Functional Polymer Coatings: Principles, Methods and Applications, Wiley Series on Polymer Engineering and Technology, John Wiley & Sons Inc, Hoboken, New Jersey, 2015.
12. Y. Lvov, B. Guo, and R.F. Fakhrullin, eds., Functional Polymer Composites with Nanoclays, Royal Soc. of Chemistry, Cambridge, 2017.
13. R. Shunmugam, ed., Functional Polymers: Design, Synthesis, and Applications, Apple Academic Press, Oakville, ON, Canada, Waretown, NJ, USA, 2017.
14. M.A.J. Mazumder, H. Sheardown, and A. Al-Ahmed, eds., Functional Polymers, Polymers and Polymeric Composites, Springer International Publishing, Cham, Switzerland, 2019.
15. V.K. Thakur and M.K. Thakur, eds., Functional Biopolymers, Polymers and Polymeric Composites, Springer International Publishing, Cham, Switzerland, 2018.
16. Subcommittee: D21.02, Standard test method for acid number of certain alkali-soluble resins, ASTM Standard D3643-15, ASTM International, West Conshohocken, PA, 2015.
17. Subcommittee: D20.10, Standard test methods for flexural properties of unreinforced and reinforced plastics and electrical insulating materials, ASTM Standard D790-17, ASTM International, West Conshohocken, PA, 2017.
18. Subcommittee: D20.10, Standard test method for Rockwell hardness of plastics and electrical insulating materials, ASTM Standard D785-08, ASTM International, West Conshohocken, PA, 2015.
19. Subcommittee: D20.10, Standard test method for tensile properties of plastics, ASTM Standard D638-14, ASTM International, West Conshohocken, PA, 2014.
20. Subcommittee: D20.50, Standard test method for water absorption of plastics, ASTM Standard D570-98, ASTM International, West Conshohocken, PA, 2018.
21. Subcommittee: F04.16, Standard practice for direct contact cell culture evaluation of materials for medical devices, ASTM Standard F813-07, ASTM International, West Conshohocken, PA, 2012.
22. Subcommittee: F04.16, Standard practice for extraction of medical plastics, ASTM Standard F619-14, ASTM International, West Conshohocken, PA, 2014.
23. Subcommittee: D30.04, Standard test method for moisture absorption properties and equilibrium conditioning of polymer matrix composite materials, ASTM Standard D5229/D5229M-14, ASTM International, West Conshohocken, PA, 2014.
24. Subcommittee: D04.46, Standard test method for effect of heat and air on a moving film of asphalt (rolling thin-film oven test), ASTM Standard D2872-12e1, ASTM International, West Conshohocken, PA, 2012.
25. Technical Committee: ISO, Workplace air quality – determination of isocyanate in air using a double-filter sampling device and analysis by high pressure liquid chromatography, ISO Standard 17736, International Organization for Standardization, Geneva, Switzerland, 2010.
26. Technical Committee: ISO, Plastics – polybutene-1 (pb-1) moulding and extrusion materials – part 1: Designation system and basis for specifications, ISO Standard 8986-1, International Organization for Standardization, Geneva, Switzerland, 2009.
27. C. Soles, Functional polymers group, electronic: https://www.nist.gov/mml/materials-science-and-engineering-division/functional-polymers-group, 2018.