Green polymer chemistry biocatalysis and materials II

Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.fw001 Green Polymer Chemistry: Biocatalysis and Materials II In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.fw001 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 ACS SYMPOSIUM SERIES 1144 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.fw001 Green Polymer Chemistry: Biocatalysis and Materials II H N Cheng, Editor Southern Regional Research Center Agricultural Research Service U.S Department of Agriculture New Orleans, Louisiana Richard A Gross, Editor Rensselaer Polytechnic Institute Troy, New York Patrick B Smith, Editor Michigan Molecular Institute Midland, Michigan Sponsored by the ACS Division of Polymer Chemistry, Inc American Chemical Society, Washington, DC Distributed in print by Oxford University Press In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.fw001 Library of Congress Cataloging-in-Publication Data Green polymer chemistry : biocatalysis and biomaterials II / H N Cheng, Richard A Gross, Patrick B Smith, editors p cm (ACS symposium series ; 1144) Includes bibliographical references and index ISBN 978-0-8412-2895-5 (alk paper) Biodegradable plastics Congresses Environmental chemistry Industrial applications Congresses Biopolymers Congresses I Cheng, H N II Gross, Richard A., 1957- III Smith, Patrick B TP1180.B55G74 2010 547′.7 dc22 2010023453 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48n1984 Copyright © 2013 American Chemical Society Distributed in print by Oxford University Press All Rights Reserved Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S Copyright Act is allowed for internal use only, provided that a per-chapter fee of $40.25 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA Republication or reproduction for sale of pages in this book is permitted only under license from ACS Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036 The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law PRINTED IN THE UNITED STATES OF AMERICA In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.fw001 Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form The purpose of the series is to publish timely, comprehensive books developed from the ACS sponsored symposia based on current scientific research Occasionally, books are developed from symposia sponsored by other organizations when the topic is of keen interest to the chemistry audience Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness When appropriate, overview or introductory chapters are added Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format As a rule, only original research papers and original review papers are included in the volumes Verbatim reproductions of previous published papers are not accepted ACS Books Department In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.pr001 Preface Green polymer chemistry is a very active area of research that has attracted the attention of the scientific community and the public at large Developments in this area are stimulated by health and environmental concerns, interest in sustainability, desire to decrease the dependence on petroleum, and opportunity to design and produce “green” products and processes A large number of publications have appeared, and many new methodologies have been reported In consideration of the rapid advances in this area, we organized an international symposium on “Green Polymer Chemistry: Biocatalysis and Biobased Materials” at the American Chemical Society (ACS) national meeting in Philadelphia, PA in August 2012 The symposium was very successful, with a total of 63 papers and active participation and discussions among the leading researchers Whereas all aspects of Green Polymer Chemistry were covered, a particular emphasis was placed on biocatalysis and biobased materials Biocatalysis involves the use of enzymes, microbes, and higher organisms to carry out chemical reactions It provides exciting opportunities to manipulate polymer structures, to discover new reaction pathways, and to devise environmentally friendly processes It also benefits from innovations in biotechnology which enables cheaper and improved enzymes to be made and customized polymeric materials to be produced in vivo using metabolic engineering Biobased materials also represent an equally exciting opportunity that has found many industrial and medical applications There is commonality with biocatalysis because many biobased products are biodegradable, where enzymes and/or microbes are involved In view of the success of the Philadelphia symposium, and the fact that this field is multidisciplinary where publications tend to be spread out over journals in different disciplines, we decided to edit this book in order to gather the information on the latest developments in one place We have asked many of the symposium presenters to contribute chapters to this book, where they report either original results or write special reviews of their ongoing work We hope this book provides a good representation of what is happening in the forefront of research in green polymer chemistry Among the 28 chapters, the following topics are covered that interweave concepts of polymers, materials, biocatalysis, and biotechnology: New biobased materials • Renewable raw materials (e.g., polysaccharides, triglycerides, lignin) • Novel bioprocesses and biobased products xi In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 proteins, Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.pr001 • • Biocatalyzed synthetic and natural polymers Silicone bioscience and biomaterials New or improved biocatalysts (e.g., enzymes, whole-cells, and cell extracts) • Improved biocatalysts (enzyme engineering, metabolic pathway engineering) • Enzyme immobilization and assembly • Enzyme-polymer bioconjugates Biotransformations with enzymes, whole cells, and cell-extracts • Polymer synthesis through biocatalysis • Grafting and functionalization reactions • Hydrolysis, degradation, and remediation Other innovative techniques • Chemo-enzymatic approaches • Genetic PEGylation • Microwave-assisted reactions It may be noted that among the 96 authors who contribute to this book, 70 work in academia, in industry, and 24 in government labs They are international in scope, with 56 from the United States, from Latin America, from Europe, and 33 from Asia This book is targeted for scientists and engineers in multiple disciplines (chemists, biochemists, chemical engineers, agronomists, biochemical engineers, material scientists, microbiologists, molecular biologists, and enzymologists) as well as graduate students who are engaged in research and applications of polymer biocatalysis and biobased materials It can also be a useful reference book for people who are interested in these topics We appreciate the efforts of the authors to submit their manuscripts and their cooperation during the peer review process We are also grateful to our many anonymous reviewers for their hard work Thanks are also due to the ACS Division of Polymer Chemistry, Inc for sponsoring the 2012 symposium H N Cheng Southern Regional Research Center Agricultural Research Service U.S Department of Agriculture 1100 Robert E Lee Blvd New Orleans, Louisiana 70124 xii In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Richard A Gross Department of Chemistry and Chemical Biology Rensselaer Polytechnic Institute Cogswell Laboratories 110 8th Street Troy, New York 12180-3590 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.pr001 Patrick B Smith Michigan Molecular Institute 1910 West St Andrews Road Midland, Michigan 48640 xiii In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Chapter Green Polymer Chemistry: A Brief Review Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch001 H N Cheng,*,1 Patrick B Smith,2 and Richard A Gross3 1Southern Regional Research Center, Agriculture Research Service, U.S Department of Agriculture, 1100 Robert E Lee Blvd., New Orleans, Louisiana 70124 2Michigan Molecular Institute, Midland, Michigan 48640 3Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New York 12180-3590 *E-mail: hn.cheng@ars.usda.gov This review briefly surveys the research done on green polymer chemistry in the past few years For convenience, these research activities can be grouped into themes: 1) greener catalysis, 2) diverse feedstock base, 3) degradable polymers and waste minimization, 4) recycling of polymer products and catalysts, 5) energy generation or minimization during use, 6) optimal molecular design and activity, 7) benign solvents, and 8) improved syntheses or processes in order to achieve atom economy, reaction efficiency, and reduced toxicity All these areas have attracted worldwide attention, with contributions variously from academic, industrial, and government laboratories Many new promising technologies are being developed Whereas most aspects of green polymer chemistry are covered in this review, special attention has been paid to biocatalysis and biobased materials due to the specific research interests of the authors Appropriate examples are provided, taken particularly from the articles included in this symposium volume © 2013 American Chemical Society In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Introduction Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch001 Green chemistry is the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances (1, 2) Because of environmental concerns, energy demands, global warming, and interest in sustainability, this concept has become very popular Several books and review articles have appeared in the past few years on this topic (1–6) There is also increasing interest in green polymer chemistry This can be seen in the number of books (7–9) and reviews (10, 11) on this topic We have previously (12) categorized the developments in green polymer chemistry into eight pathways (Table 1) These pathways also appear to be consistent with most of themes discussed in recent articles and books on green chemistry (1–6) Table Major pathways for green polymer chemistry Major Pathways Examples Greener catalysts Biocatalysts, such as enzymes and whole cells Diverse feedstock base Biobased building blocks and agricultural feedstock (sugars, peptides, triglycerides, lignin) Natural fillers in composites CO2 as monomer Degradable polymers and waste minimization Natural renewable materials Some polyesters and amides Recycling of polymer products and catalysts Many degradable polymers can potentially be recycled Immobilized enzymes can be reused Energy generation or minimization of use Biofuels Reactive extrusion method Microwave-assisted synthesis Optimal molecular design and activity Improved enzymes Metabolic engineering Protein synthesis Benign solvents Water, ionic liquids, or reactions without solvents Improved syntheses and processes atom economy, reaction efficiency, toxicity reduction The aim of this article is not to provide a comprehensive review of green polymer chemistry but to highlight major developments in this area, using selective literature and emphasizing research reported in this symposium volume (13–39) A particular emphasis is placed on biocatalysis (e.g., (40–47)) and biobased materials (e.g., (48–55)) Biocatalysis involves the use of enzymes, microbes, and higher organisms to facilitate chemical reactions Because the reaction conditions are often mild, water-compatible, and environmentally friendly, they are good examples of green polymer chemistry Likewise, many biobased materials are biodegradable and recyclable, and their use represents an exemplar of green polymer chemistry In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Table Mechanical properties of LDPE-burr-compatibilizer compositesa Description Thickness (mm) Tensile Strength (N/mm2) Elongation (%) Young’s Modulus (MPa) LDPE 1.91 (0.05) 6.8 (0.1) 287 (45) 31 (2) LDPE + C1 1.70 (0.02) 6.6 (0.04) 228 (37) 32 (2) LDPE + C2 1.75 (0.03) 7.0 (0.1) 286 (48) 30 (1) LDPE + C3 1.79 (0.06) 6.5 (0.1) 270 (-)b 30 (1) LDPE + C4 1.85 (0.03) 6.5 (0.1) 293 (26) 32 (2) LDPE + F1 1.74 (0.02) 5.5 (0.2) 100 (15) 31 (1) 10 LDPE + F1 + C1 1.70 (0.03) 6.2 (0.2) 105 (34) 33 (1) 14 LDPE + F1 + C2 2.23 (0.05) 6.3 (0.1) 126 (13) 29 (1) 18 LDPE + F1 + C3 1.89 (0.01) 5.8 (0.1) 110 (14) 29 (1) 22 LDPE + F1 + C4 2.03 (0.07) 5.7 (0.2) 96 (19) 29 (1) LDPE + F2 1.52 (0.04) 3.7 (0.1) 31 (3) 43 (2) 11 LDPE + F2 + C1 1.66 (0.05) 4.5 (0.1) 26 (2) 43 (1) 15 LDPE + F2 + C2 1.63 (0.03) 4.4 (0.3) 36 (5) 39 (2) 19 LDPE + F2 + C3 1.84 (0.03) 3.7 (0.1) 38 (5) 37 (0.3) 23 LDPE + F2 + C4 1.78 (0.01) 3.6 (0.2) 25 (2) 43 (2) LDPE + F3 1.62 (0.12) 3.5 (0.1) 32 (3) 39 (2) 12 LDPE + F3 + C1 1.61 (0.01) 4.1 (0.2) 24 (2) 37 (1) 16 LDPE + F3 + C2 1.69 (0.05) 3.5 (0.04) 31 (2) 34 (1) 20 LDPE + F3 + C3 1.80 (0.04) 3.2 (0.03) 32 (2) 35 (2) 24 LDPE + F3 + C4 1.83 (0.03) 3.3 (0.1) 30 (2) 36 (2) LDPE + F4 1.55 (0.09) 3.4 (0.2) 27 (3) 35 (3) 13 LDPE + F4 + C1 1.64 (0.23) 3.8 (0.2) 24 (2) 33 (2) 17 LDPE + F4 + C2 1.72 (0.05) 3.0 (0.3) 20 (4) 29 (1) 21 LDPE + F4 + C3 1.83 (0.20) 3.1 (0.2) 24 (4) 30 (2) 25 LDPE + F4 + C4 1.87 (0.04) 3.5 (0.1) 22 (3) 36 (2) Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch028 Sample No a Standard deviations are given in parentheses Compatibilizer C1 = polyethylene grafted with wt% maleic anhydride; C2 = polyethylene methacrylic acid random copolymer (15% methacrylic acid); C3 = polyethylene-acrylic acid copolymer (15 wt% acrylic acid); C4 = polyethylene-acrylic acid copolymer (5 wt% acrylic acid) b Data partly lost 427 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch028 The mechanical properties of LDPE composites shown for burr fraction F2 as samples 7, 11, 15, 19, and 23; for burr fraction F3 as samples 8, 12, 16, 20, and 24; and for burr fraction F4 as samples 9, 13, 17, 21, and 25 (Table 2) LDPE with the burr fractions F2, F3, or F4 alone (samples 7, 8, and 9, respectively) had lower tensile and elongation but higher Young’s modulus than LDPE without filler (sample 1) This was consistent with our earlier study of LDPE blended with cotton burr (24) The mechanical properties of LDPE-burr composites with compatibilizers C3 and C4 did not show noticeable improvements over the LDPE-burr composites without compatibilizers However, incorporation of the compatibilizers C1 and C2 seemed to have beneficial effects on tensile strength for most of the samples Elongation was not affected and the Young’s modulus either stayed the same or was slightly reduced with the inclusion of compatibilizers C1 and C2 The effect of burr particle size on the mechanical properties can be seen by plotting tensile strength, elongation, and Young’s modulus separately (Figures 1–3) It may be reminded that for F1 the filler level was 3%, whereas for F2, F3, and F4, the filler level was 25% Moreover, the average particle size for fillers decreased in the order F1 > F2 > F3 > F4 Thus, an increasing value on the x-axis in Figures 1–3 represents decreasing particle size The tensile strength of the composites decreased by about 10% when fraction F1 was added at 3%, but decreased to about 50% when 25% of F2, F3, or F4 was added (Figure 1) As filler particle size decreased (from F2 to F4), tensile strength also decreased slightly (Figure 1) This weakening of the composites was probably due to poor bonding between filler particles and LDPE polymer, with each particle serving as a weak point that reduces tensile strength At the same 25% filler level, filler with smaller particles contain more particles resulting in greater surface areas with the base polymer, thereby leading to more weak points The use of compatibilizer partly remedied this effect Compatibilizer C1 appeared to have the most beneficial effect, followed by compatibilizer C2 Elongation decreased as filler was added (Figure 2), similar to the trends observed with tensile strength The effect of filler particle size and compatibilizer addition on elongation was less apparent Different behavior was observed for the Young’s modulus (Figure 3), which exhibited a maximum with burr fraction F2 but decreased with fractions F3 and F4 This indicates that the presence of larger filler particles enhances the stiffness of LDPE; but if the filler particles are too small, they became less effective in stiffening the polyethylene matrix The addition of a compatibilizer did not appear to be beneficial for Young’s modulus; among the four compatibilizers, C1 gave the best results Thus, the addition of cotton burr fractions F2, F3, and F4 as fillers in LDPE reduced tensile strength and elongation but generally improved the Young’s modulus of the composites The use of C1 and C2 compatibilizers improved tensile strength in most samples Filler particle size had an important effect on the composite’s mechanical properties In particular, the Young’s modulus of the composite could be optimized by using filler with an appropriate particle size 428 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch028 Figure Effect of filler size on tensile strength of LDPE composites: LDPE (no compatibilizer), solid brown line, diamond markers; LDPE with C1, dotted black line, square markers; LDPE with C2, short dashed green line, triangle markers; LDPE with C3, long dashed purple line, X markers; LDPE with C4, dashed-dotted blue line, * markers On x-axis, F = LDPE without filler Figure Effect of filler size on elongation for LDPE composites: LDPE (no compatibilizer), solid brown line, diamond markers; LDPE with C1, dotted black line, square markers; LDPE with C2, short dashed green line, triangle markers; LDPE with C3, long dashed purple line, X markers; LDPE with C4, dashed-dotted blue line, * markers On x-axis, F = LDPE without filler 429 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch028 Figure Effect of filler size on Young’s modulus for LDPE composites: LDPE (no compatibilizer), solid brown line, diamond markers; LDPE with C1, dotted black line, square markers; LDPE with C2, short dashed green line, triangle markers; LDPE with C3, long dashed purple line, X markers; LDPE with C4, dashed-dotted blue line, * markers On x-axis, F = LDPE without filler In summary, LDPE-cotton burr composites have modified properties that may serve some niche uses If there is an application for LDPE where a stiffer and somewhat cheaper material is needed, the use of cotton burr filler with a compatibilizer may be considered Acknowledgments The authors would like to thank Janet Berfield for technical assistance, and Gary Grose and Paulette Smith for help with extrusion Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S Department of Agriculture USDA is an equal opportunity provider and employer References Xanthos, M Functional Fillers for Plastics; Wiley-VCH: Weinheim, Germany, 2010 Wool, R P.; Sun, X S Bio-Based Polymers and Composites; Elsevier: Burlington, MA, 2005 Bledzki, A K.; Reihmane, S.; Gassan, J Polym.-Plast Technol Eng 1998, 37 (4), 451–468 Peanasky, J S.; Long, J M.; Wool, R P J Polym Sci.: Part B: Polym Phys 1991, 29, 565–579 and references therein 430 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ch028 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Albertsson, A.-C.; Barenstedt, C.; Karlsson, S J Appl Polym Sci 1994, 51, 1097–1105 Willett, J L J Appl Polym Sci 1994, 54, 1685–1695 Willett, J L Polym Eng Sci 1995, 35, 1184–1190 Arvanitoyannis, I.; Biliaderis, C G.; Ogawa, H.; Kawasaki, N Carbohydr Polym 1998, 36, 89–104 Yoo, Y.-D.; Kim,Y.-W.; Cho, W.-Y U.S Patent 5,461,093 Girija, B G.; Sailaja, R R N J Appl Polym Sci 2006, 101 (2), 1109–1120 Gupta, A P.; Kumar, V.; Sharma, M.; Shukla, S K Polym.-Plast Technol Eng 2009, 48 (6), 587–594 Gupta, A P.; Kumar, V.; Sharma, M J Polym Environ 2010, 18, 484–491 Kim, T.-J.; Lee, Y.-M.; Im, S.-S Polym Compos 1997, 18 (3), 273–282 Ołdak, D.; Kaczmarek, H.; Buffeteau, T.; Sourisseau, C J Mater Sci 2005, 40 (16), 4189–4198 Kaczmarek, H.; Ołdak, D Polym Degrad Stab 2006, 91 (10), 2282–2291 Lomakin, S M.; Rogovina, S Z.; Grachev, A V.; Prut, E V.; Alexanyan, C V Thermochim Acta 2011, 521, 66–73 de Menezes, A J.; Siqueira, G.; Curvelo, A A S.; Dufresne, A Polymer 2009, 50, 4552–4563 Tajeddin, B.; Rahman, R A.; Abdulah, L C.; Ibrahim, N A.; Yusof, Y A Eur J Sci Res 2009, 32 (2), 223–230 Madera-Santana, T J.; Robledo, D.; Azamar, J A.; Rios-Soberanis, C R.; Freile-Pelegrin, Y Polym Eng Sci 2010, 50 (3), 585–591 Raj, R G.; Kokta, B V.; Nizio, J D J Appl Polym Sci 1992, 45 (1), 91–101 Beyer, C D US Patent 5,755,836 Sutivisedsak, N.; Cheng, H N.; Burks, C S.; Johnson, J A.; Siegel, J P.; Civerolo, E L.; Biswas, A J Polym Environ 2012, 20, 305–314 Sutivisedsak, N.; Cheng, H N.; Liu, S.; Lesch, W C.; Finkenstadt, V L.; Biswas, A J Biobased Mater Bioenergy 2012, (1), 59–68 Sutivisedsak, N.; Cheng, H N.; Dowd, M K.; Selling, G W.; Biswas, A Ind Crops Prod 2012, 36, 127–134 Bailey, A E Cottonseed and Cottonseed Products; Wiley-Interscience: New York, 1948; pp 873−893 Hausmann, K In Concise Polymeric Materials Encyclopedia; Salamone, J C., Ed.; CRC Press: Boca Raton, FL, 1999; pp 273–276 Koning, C.; Van Duin, M.; Pagnoulle, C.; Jerome, R Prog Polym Sci 1998, 23, 707–757 Bicerano, J A Practical Guide to Polymeric Compatibilizers for Polymer Blends, Composites and Laminates www.plas2006.com/UploadFile/ TopicFile/20063112235119.doc 431 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Subject Index A Aliphatic polyesters, syntheses and characterization, 59 ATRPases, 165 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 B Biocatalysis for silicone-based copolymers 1,3-bis(3-carboxypropyl) tetramethyldisiloxane, lipase (Novozym-435®) catalyzed copolymerization, 104s polysiloxanes, 97 silicone aliphatic polyesteramides, 99 silicone aliphatic polyesters, 98 silicone aromatic polyamide (SAPA), lipase (Novozym-435®) catalyzed synthesis, 102s silicone aromatic polyesters and polyamides, 100 silicone fluorinated aliphatic polyesteramides, 99 silicone polycaprolactones, 102 silicone polyethers, 103 silicone sugar conjugates, 104 stereo-selective organosiloxanes, 105 Biocatalytic atom transfer radical polymerization (ATRP), 163 ARGET ATRP of PEGA catalyzed cys-blocked Hb, 167f characterization of HRP, 168f hemoglobin (cys-blocked Hb) or horseradish peroxidase (HRP), 166f Biofuel synthesis and biological fuel cells, 18 Biosilicification, 95 Bisphenol polymers and copolymers, green synthesis, 121 C Candida antarctica lipase B (CALB), 29, 73, 82 Converting polysaccharides into high-value thermoplastic materials melt rheology, 409 modified starch, water-dispersible thermoplastic materials, 410 modified starch conversion into thermoplastic modified starch, 409 tensile properties, 409 tertiary water-dispersible films, water-dispersibility, 419 thermoplastic modified starch, binary polymer blends, 411 thermoplastic modified starch blends ductility, 413f peak stress, 412f thermoplastic modified starch ether (TPSE)/copolyester blends, ductility, 414f water disintegration, 410 water-dispersible films, water disintegration test results, 420t water-dispersible films with balanced mechanical properties effects of copolyester level, 417 tertiary blend films, 415 water-dispersible tertiary blend films ductility, 417f, 418f modulus, 416f peak stress, 416f, 418f Cottonseed isolate solubility profiles, 355 D Direct fluorination of poly(3hydroxybutyrate-co)-hydroxyhexanoate, 291 direct fluorination reactor, 297f effect of fluorination, 300 evidence of fluorination, 298 fluorine containing PLAs and PHAs, 294 future prospective, 300 neat PHA and F-PHA, XPS and ATR-FTIR spectra, 299f PHA synthesis and development, general lifecycle, 293f PLA endcapped and enchained fluoropolymers, 295f using 5% F2 in N2 gas mixture, general procedure, 296 fluorination of PHA polymers, 298 typical procedure, 298 441 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 E Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 Enzyme-based technologies, 15 antifouling coatings, 21 bioactive coatings, 20 conclusions and future directions, 22 decontamination coatings, 21 enzymes as biosensors, 19 enzymes for energy, 18 industrial catalysis, 16 enzymes as biological catalysts, applications, 17f layered technology, 23f F Food and biobased materials, applications of common beans, 331 bean extrudates, water absorption index (WAI), 333t common bean as filler in polymers LDPE filler, 335 PLA filler, 334 PVOH filler, 336 common beans, extrusion cooking, 332 conversion of bean starch to ethanol, 338 phenolic phytochemicals in common beans, 338 triglyceride oils in common beans, 337 individual peptides/proteins, separation, 351f solubility (% soluble protein) of isolates prepared, 352t cottonseed proteins, application and potential use, 356 functional characterization of isolates emulsification properties, 347 foaming properties, 347 solubility profiles, 346 surface hydrophobicity index (So), 346 water-holding capacity, 347 isolate and meal characterization, 345 isolate preparation, 345, 353 isolate properties, 354 isolate yield and composition and color, 349 Green polymer chemistry, major pathways, 2t pathways Benign solvents, biocatalysts, degradable polymers and waste minimization, diverse feedstock base, energy generation and minimization of use, improved syntheses and processes, molecular design and activity, polymer products and catalysts, recycling, G Genus Thermobifida, polyester-degrading cutinases, 111 assay of enzymatic activity, 113 circular dichroism (CD) and differential scanning calorimetry (DSC), measurement, 113 cloning, expression, and purification, 113 crystallography of Est119, 118 3D structure of Est119, 117f homology modeling, 113 mutagenesis, 116 recombinant Est1 and Est119, characterization and mutational analysis, 115 tandem cutinase genes, 114 Glandless and glanded cottonseed, protein isolate, 343 amino acid composition (g/100 g protein), 350t H Hydrogenated cottonseed oil, 359 hydrogenation kinetics, modeling, 365 Ni-catalyzed hydrogenation composition of stearic, oleic, TFA, and linoleic, 363f kinetic modeling of hydrogenation data, 366f Pd-catalyzed hydrogenation composition of stearic, oleic, TFA, and linoleic, 364f kinetic modeling of hydrogenation data, 366f Pt-catalyzed hydrogenation composition of stearic, oleic, TFA, and linoleic, 364f kinetic modeling of hydrogenation data, 367f utility, 368 Hydrogenation of cottonseed oil, 362 442 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 L Laccase and linear-dendritic block copolymers, supramolecular complexes, 121 experimental flow chart of procedures, 125s instrumentation, 124 laccase modification, 124 materials, 123 polymerization reactions, 124 introduction, 122 bisphenol A, 127 bisphenols polymerized with laccase/LD copolymer complex, 126s BPA and DES, copolymerization, 135 BPA and DES polymerization, differences, 132 diethylstilbestrol, 131 FT-IR spectra of monomer, DES, and polymer, poly-DES, 136f oxidized DES, molecular weight, 132f poly-BPA, bonding, 130 poly-BPA, molecular weight, 128f, 129 SEC chromatograms of products, 134f Lignin-based graft copolymers, 373 alkyne functionalized lignin, preparation, 377 alkyne functionalized lignin and unmodified native lignin, 385f ATRP graft-copolymerization of poly(n-butyl acrylate), 383f ATRP graft-copolymerization of polystyrene, 381f azide functionalized polystyrene, preparation, 377 click chemistry graft copolymerization of lignin and polystyrene, 387 lignin-graft-polystyrene preparation, 378 GPC characterization, 378 graft copolymerization (ATRP) of styrene and n-butyl acrylate, 376 graft onto method alkyne functionalized lignin preparation, 384 azide functionalized polystyrene preparation, 386 1H NMR characterization, 378 lignin-based macroinitiator, preparation, 376 lignin-based macroinitiator for ATRP, 380f lignin-graft-poly(n-butyl acrylate), preparation, 382 preparation of lignin ATRP macroinitiator and lignin-graftpolystyrene, 379 Lipase-catalyzed synthesis, 29 carbonyl carbon-13 NMR absorptions, 36f copolymerization of diesters with amino-substituted diols, 32s diesters and amino-substituted diols, polycondensation, 31 ω-hydroxy β-amino ester EHMPP, synthesis, 38s lactone-DES-MDEA terpolymer properties, 37 lactone-DES-MDEA terpolymers characterization, 35t synthesis, 34s molecular weight and isolated yield of poly(amine-co-esters), 32t PDL-DES-MDEA terpolymers, diad distributions, 37t PMPP and poly(PDL-co-MPP), enzymatic synthesis, 39s poly(amine-co-ester) properties, 33 poly(amine-co-ester) terpolymers, synthesis and structures, 33 poly(PDL-co-MPP) copolymers diad distributions, 40t properties, 40 poly[Ω-pentadecalactone-co-3(4-(methylene)piperidin-1yl)propanoate] (poly(PDL-co-MPP)), synthesis and structures, 38 product molecular weight and polydispersity, variations, 36t purified Poly(PDL-co-MPP), characterization, 40t M Microwave-assisted biocatalytic polymerizations, 73 enzymatic polymerizations, 74 lipase, 74 organic synthesis, 70 ω-pentadecalactone, polymerization, 76t polymer synthesis, ring opening polymerization (ROP), 72 ROP of caprolactone, 75f Microwave-assisted organic synthesis, 70 Cannizzaro Reaction, 71 Suzuki and Heck Reactions, 71 443 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 N New lactate-based biopolymers, 175 abbreviations, 193 conclusions and future perspectives, 192 copolymerization of other monomers with LA, 183 Corynebacterium glutamicum, P(LA-co-3HB) production, 190 engineering of other PHA synthases, 191 LA units in P(LA-co-3HB) polymers, enrichment further engineering of LPE, 182 use of metabolically engineered E coli and anaerobic culture conditions, 181 LA-based polymer production, 176 lactate-polymerizing enzyme (LPE), 176 discovery, 178 discovery to drive MPF, 179 microbial plastic factory, 180 polyhydroxyalkanoates (PHAs), 176 properties LA in P(LA-co-3HB), enantiomeric purity, 186 P(LA-co-3HB)s, mechanical properties, 189 polymer sequence and molecular weight, 189 thermal and mechanical properties, 188t thermal properties and transparency, 187 synthesis of P(96 mol% LA-co-3HB-3HV), 185 synthesis of P(LA-co-3HB-co-3HHx), 184f O OAC See Oil absorption capacity (OAC) Oil absorption capacity (OAC), 333 P PEGylated antibodies and DNA conclusions and future outlook, 231 genetic PEGylation, 229 DNA templates, preparation, 230f PEGylated antibody in organic media, 224 list of antibodies used, 225t unmodified and PEGylated antibodies, solubility, 225t PEGylated DNA in organic media, 226 PEG–DNA–hemin complex, peroxidase activity, 228f PEG-modified DNA sequences, 227t PHA production, types, 213t PHA synthase from marine bacteria, 218 Phosphorylase-catalyzed enzymatic α-glycosylations amylose production, 147f amylose-grafted cellulose, chemoenzymatic synthesis, 155f amylose-grafted heteropolysaccharides chemoenzymatic synthesis, 154f synthesis, 153 amylose-grafted sodium carboxymethyl cellulose (NaCMC) alkaline solution, 157f chemoenzymatic synthesis, 156f anionic glycogen, 152f characteristic features, 145 dissolution, re-hydrogelation, and suppression, 150f enzymatic glycosylation, 143f GlcA residues, 151 glucose substrates, glycosylation, 142f glycosyl donor, 146f glycosyl hydrolases, 144 highly branched polysaccharide materials, preparation, 148 hydrogel formation, 149f Leloir glycosyltransferases, 144 PMMA See Poly(methyl methacrylate) (PMMA) Polyethylene composites, use of cotton gin trash and compatibilizers, 423 effect of burr particle size, mechanical properties, 428 LDPE-burr-compatibilizer composites composition, 426t effect of filler size on elongation, 429f effect of filler size on tensile strength, 429f effect of filler size on young’s modulus, 430f mechanical properties, 427t Poly(ethylene glycol)s under solventless conditions, enzymatic functionalization, 81 acrylation product of PEG, NMR spectra, 89f CALB-catalyzed transesterification, 83 methacrylation product of PEG, 87f PEG dimethacrylate, MALDI-ToF mass spectrum, 88f 444 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 PEG-dicrotonate MALDI-ToF mass spectrum, 92f NMR spectra, 91f telechelic polymers, enzymes in synthesis, 85 transesterification of vinyl crotonate with PEG, 90, 91s vinyl acetate, transesterification, 84f vinyl acrylate and vinyl methacrylate, transesterification, 86 Poly(3-hydroxybutyrate-co-3hydroxyvalerate) (PHBV), biodegradable films and foam, 251 average distance between PHBV nuclei, 263t characterization of PHBV adjusted foam bulk density, shrinkage of P99S1 foams, 275t bulk density and cell density, 273f impact of SF on PHBV foam density and cell density, 272 overall impact of SF content, 275 shrinkage, 274 crystallinity of PHBV and SF versus blend composition, 264f degradation temperatures determined from TGA, 260t experimental materials and methods film morphology characterization, 256 foam characterization, 257 PHBV/SF film preparation, 255 PHBV/SF foam processing, 256 silk fibroin aqueous solutions, 254 silk gelation and powder preparation, 254 thermal analysis of films, 255 PHBV/SF, structure and property development fast cooling from melt, 266 film casting, 265 PHBV/SF blend films, characterization glass transition, 257 melting and crystallization properties, 259 morphology, 261 second heating cycle, 258f thermal degradation, 260 thermal properties, 259t silk gelation process development, powder production, 267 cycle of freezing, achieve gel, 269f freeze-thaw cycling schemes, 270t impact of temperature, time, and cycling, 270 multiple freeze-thaw cycling for SF gelation, 268 β-sheet, 271 single freeze-thaw cycle for SF gelation, 268 spherulitic formation, 262f Poly(methyl methacrylate) (PMMA), 45 Poly-(R)-3 hydroxyoctanoate (PHO) and its graphene nanocomposites, 199 effect of TRG loading on thermal transitions of PHO, 205t electrical properties, 207 graphene production and characterization, 201 mechanical properties, 206 morphology PHO-TRG nanocomposites, 204 nanocomposites, fabrication and characterization, 201 PHO synthesis, 200 PHO-TRG nanocomposites, mechanical properties, 206t production and characterization of TRG, 203 pseudomonas oleovorans, PHO synthesis, 203f purified PHO, preparation, 202 thermal properties, 204 S Silk fibroin (SF), 253 Soybean biorefinery, biobased industrial products, 305 dimer fatty acids, isocyanate-free poly(amide-urethane)s, 320 dimer acid, P1, ethylene carbonate, P2 and P3, 322f synthesis, general approach, 321f polyols by ozonation of soybean oil, 309 generalized ozonolysis reaction, 310f polyols composition of triglycerides, 311f statistical distribution of soy polyols, 312f polyols from soymeal, 313 amino acids, 316 end-group analysis, 315t hydroxyl-terminated urethane pre-polymers, preparation, 314f polymeric methylene diphenyl diisocyanate (MDI), 316 properties of rigid foams, 316 properties of rigid PU foams prepared from soymeal urethanep olyols, 318t silylated soybean oil, coatings, 323 445 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 enzyme catalyst surface stability, evaluation, 44 microfluidic reactor, 54 reaction monitoring, 50 ring-opening polymerization, engineering control, 53 summary and outlook, 55 two-dimensional crosslinked PMMA thin film, 46s understanding kinetic pathways, 47 alkoxysilanes, 325 grafting VTMS onto soy oil, 324f moisture activated cure mechanism, 326f typical formulation of rigid foams derived from L-arginine-polyol, 317t typical soybean oil fatty acid composition, 307t value-added industrial products, 308f Structure and thermal properties of poly(caffeic acid), polycondensation conditions, 237 CA and PCAs, solubility, 242t experimental instrumentation, 240 materials, 239 synthesis of PCA, 239 MALDI-TOF-MS spectra of PCA1 and ACA, 243f molecular structure, solubility, and molecular weight distribution of PCAs, 241 optical micrographs of PCAs, 245f thermal and mechanical properties of PCA, 244 thermal durability of PCAs, 246 V T X Trimethylolpropane and adipic acid, hyperbranched polyesters bimolecular nonlinear polymerization (BMNLP) methodology, 282 copolymer of TMP and AA, 285f hyperbranched copolymer of TMP and AA, 286f kinetic analysis, 287 function of catalyst level, 288 materials and methods, 283 NMR assignments, 284 Xylan esterification and its application, 393 crystallization studies, 401 GPC data of xylan esters, 397t haze measurement, 395 isothermal crystallization, 395, 403 materials, 394 mechanical properties, 398 non-isothermal crystallization, 395, 401 PLLA and PLLA blend t1/2 values, effect of varying Tc values, 404f thermal data, 402t polarized optical microscopy (POM), 395 spherulite morpholgy, crystallinity, and haze, 403 stress-strain test, 395 syntheses, molecular weight, and structure analyses, 396 syntheses of xylan ester, 394 thermal and WAXD analyses, 399 WAXD data of xylan ester films, 400t wide-angle x-ray diffraction (WAXD), 395 Vibrio sp strain, polyhydroxyalkanoate biosynthesis, 211 accumulations using different carbon sources, 214t accumulations using three types of unsaturated fatty acids, 218t fatty acids compositions of plant oil, 216t using plant oil, 215 using sugars and organic acid, 213 using unsaturated fatty acids, 217 U Understand immobilized enzyme catalyzed ring-opening polymerization ε-caprolactone, enzyme-catalyzed polymerization, 48s ε-CL ring-opening conversion, 49f enzymatic copolymerization of ε-CL and δ-VL monomer concentration profiles, 51f monomer fraction versus total monomer conversion, 52f 446 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Y Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ix002 Yarrowia lipolytica lipase biocatalysis, 59 experimental α-hydroxyl-ω-(carboxylic acid) poly(ε-caprolactone), synthesis, 61 instrumentation, 60 materials, 60 PCL macrodiisocyanate, synthesis, 62 α,ω-telechelic poly(ε-caprolactone) diols (HOPCLOH), synthesis, 61 α-hydroxyl-ω-(carboxylic acid) poly(ε-caprolactone), 62 poly(ε-caprolactone) diols, bisubstitution, monosubstitution, 65t polyester-urethanes, mechanical properties, 66t, 67t synthesis of oligomer, incorporation of e-caprolactone, 65f synthesized poly(ε-caprolactone) diols, molecular weights, 64t α,ω-telechelic poly(ε-caprolactone) diols (HOPCLOH), synthesis, 63 447 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Editors’ Biographies Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ot001 H N Cheng H N Cheng (Ph.D., University of Illinois) is currently a research chemist at Southern Regional Research Center of the U.S Department of Agriculture in New Orleans, where he works on projects involving improved utilization of commodity agricultural materials, green chemistry, and polymer reactions Prior to 2009 he was with Hercules Incorporated where he was involved (at various times) with new product development, team and project leadership, new business evaluation, pioneering research, and supervision of analytical research Over the years, his research interests have included NMR spectroscopy, polymer characterization, biocatalysis and enzymatic reactions, functional foods, and pulp and paper technology He is an ACS and a POLY Fellow and has authored or co-authored 174 papers, 24 patent publications, co-edited books, and organized or co-organized 22 symposia at national meetings since 2003 Richard A Gross Professor Richard A Gross (Ph.D., Polytechnic University) was on the faculty of University of Massachusetts (Lowell) from 1988−1998 From 1998 to June 2013 he occupied the Herman F Mark Chair Professorship at Polytechnic University (New York) Since July 1, 2013 Gross assumed a Constellation Chaired Professorship at Rensselaer Polytechnic Institute (RPI) and is also a member of RPI’s Departments of Chemistry and Biology as well as Biomedical Engineering His research is focused on developing biocatalytic routes to biobased materials including monomers, macromers, prepolymers, polymers, surfactants, and other biochemicals He combines chemical methods with cell-free and whole-cell biocatalytic systems to investigate biotransformations, such as whole-cell routes to biosurfactants, ω-hydroxylation of fatty acids, protease-catalyzed transformations to polypeptides, and lipase-catalyzed routes to biomaterials He has over 400 publications in peer-reviewed journals, has been cited approximately 7000 times, has edited books, and has granted and filed a total of 26 patents Gross has founded and directed several major research centers and assumed a large number of editorial assignments He is also the recipient of numerous awards, including the 2003 Presidential Green Chemistry Award in the academic category In 2007, he was inducted into the American Institute for Medical and Biological Engineering In 2010, he was selected as the Turner Alfrey Visiting Professor He founded SyntheZyme, LLC in 2009 and serves as its Chief Technology officer SyntheZyme was established to commercialize technologies developed in Gross’s laboratory © 2013 American Chemical Society In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Patrick B Smith Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ot001 Patrick B Smith currently serves as a Research Scientist at Michigan Molecular Institute He received a Ph.D in Physical Chemistry from Michigan State University and joined The Dow Chemical Company, rising to the rank of Fellow prior to his retirement in 2007 During his time at Dow, he served with Cargill Dow Polymers which launched the IngeoTM line of poly(lactic acid) products He consulted for Archer Daniels Midland (ADM) between 2007and 2010, as their R&D leader for the Telles joint venture that commercialized poly(hydroxyalkanoates) and on ADM’s biobased propylene glycol effort He was elected as ACS Fellow in 2013 436 In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Publication Date (Web): November 22, 2013 | doi: 10.1021/bk-2013-1144.ot002 Epilogue Thus far, with a tired but eager pen, The editors have pursued their story, Where enzymes are showcased time and again In examples that boast of their glory Like magic potions that were once believed, They have charmed both research and industry; Through them improved reactions are achieved With less waste and more skillful chemistry Likewise, biobased know-how is the best thing In material science right now that we need Its vogue is due to prudent managing That permits many projects to proceed We celebrate both fields in this book And hope that you agree with our outlook H N Cheng June 2013 (A parody on William Shakespeare’s Henry V, Epilogue) © 2013 American Chemical Society In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 ... Poly(3-hydroxybutyrate-co)-hydroxyhexanoate In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H N., In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium... A Green Synthesis of Bisphenol Polymers and Copolymers, Mediated by Supramolecular Complexes of Laccase and Linear-Dendritic Block Copolymers In Green Polymer Chemistry: Biocatalysis and Materials. .. green polymer chemistry In Green Polymer Chemistry: Biocatalysis and Materials II; Cheng, H., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013 Green Polymer Chemistry: