Handbook of SUSTAINABLE POLYMERS This page intentionally left blank 1BO4UBOGPSE4FSJFTPO3FOFXBCMF&OFSHZ7PMVNF Handbook of SUSTAINABLE POLYMERS Structure and Chemistry editors Preben Maegaard Anna Krenz Wolfgang Palz edited by Vijay Kumar Thakur Manju Kumari Thakur The Rise of Modern Wind Energy Wind Power for the World CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2016 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20160419 International Standard Book Number-13: 978-981-4613-56-9 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com To my parents and teachers who helped me become what I am today Vijay Kumar Thakur This page intentionally left blank Contents Preface Sustainable Polymers: A Perspective to the Future Vijay Kumar Thakur and Manju Kumari Thakur 1.1 1.2 1.3 1.4 1.5 xxvii Introduction Natural Cellulose Fibers Chitosan Guar Gum Starch Properties of Natural Cellulose Fibers and Methods of Their Modification for the Purpose of Paper Quality Improvement Konrad Olejnik, Anna Stanislawska, and Agnieszka Wysocka-Robak 2.1 Introduction 2.2 Characteristics of Cellulose Fibers Used for Paper Production 2.2.1 Properties of Fibers from Different Wood Species and Different Processes 2.2.1.1 Fiber properties of different wood species 2.2.1.2 Properties of pulps from different processes 2.2.2 Molecular Level Properties 2.2.3 Fiber Properties 2.2.3.1 Water sorption and swelling 2.2.3.2 Fiber charge 2.2.3.3 Flocculation 2.2.3.4 Fiber bonding and formation of paper structure 1 12 14 15 19 19 20 20 22 23 25 28 31 35 37 38 viii Contents 2.3 2.4 2.5 2.6 2.2.3.5 Shrinkage Methods of Cellulose Fiber Modification for Papermaking Purposes 2.3.1 Refining 2.3.2 Enzymatic Treatment 2.3.2.1 Cellulases 2.3.2.2 Hemicellulases Chemical Additives for Fiber–Fiber Bonding Improvement 2.4.1 Improvement of Fiber–Fiber Bonding in Dry State 2.4.1.1 Importance of dry-strength additives 2.4.1.2 Natural dry-strength additives 2.4.1.3 Synthetic dry-strength additives 2.4.2 Improvement of Fiber–Fiber Bonding in Wet State 2.4.2.1 Development of wet-strength 2.4.2.2 Wet-strengthening in acid conditions 2.4.2.3 Wet-strengthening in neutral and alkaline conditions Future Technologies 2.5.1 Deep Eutectic Solvents 2.5.2 Microfibrillated Cellulose Summary New Use for an “Old” Polysaccharide: Pectin-Based Composite Materials Rascón-Chu Agustín, Díaz-Baca Jonathan A., Carvajal-Millán Elizabeth, López-Franco Yolanda, and Lizardi-Mendoza Jaime 3.1 Pectin: History and Overview 3.2 Pectin Types 3.3 Chemical Structure 40 42 42 46 47 48 51 52 53 53 55 57 58 59 60 62 62 62 63 71 72 73 74 Contents 3.4 3.5 3.6 3.7 Physicochemical Properties Gelling Properties In vivo Function Sources of Pectins 3.7.1 New and Atypical Sources of Extraction 3.7.2 Agroindustrial Wastes as Sources of Extraction 3.8 Applications 3.8.1 Traditional Applications 3.8.2 Pectin as a Dietary Supplement 3.8.3 Pectins as Drug Controlled Delivery Systems 3.8.4 Pectin as Prebiotic 3.9 Composite Structures 3.9.1 Pectin–Protein Composite Matrices 3.9.1.1 Pectin–protein interactions 3.9.1.2 Properties of complex composites 3.9.1.3 Fabrication of composite matrices 3.9.2 Pectin–Lipid Composite Matrices 3.9.2.1 Liposomes 3.9.2.2 Pectin–liposome structures 3.9.2.3 Oily bodies 3.10 Conclusion Chemically Modified Lignin and Its Application in Oil and Gas Drilling Industry Mohamed Rashid Ahmed Haras, Mohamad Nasir Mohamad Ibrahim, and Rohana Adnan 4.1 Lignin 4.1.1 General Description 4.1.2 Structure of Lignin 4.1.3 Types of Lignin 4.1.4 Potential Industrial Applications 4.1.5 Previous Studies 4.1.6 Source of Lignin in This Study 4.2 Oil Palm 76 76 78 78 79 82 85 85 86 88 88 89 90 90 91 92 93 94 95 96 97 109 109 109 111 112 113 114 115 116 ix SAS Polymer Precipitation Process even to 70 nm at higher operating conditions than other works where different types of acrylic polymers were processed as well by the SAS process in the micrometer range at no very high operating conditions in the vessel [43, 67] These polymer nanoparticles could be used to obtain drug–polymer nanosystem that could penetrate the physiological membranes to get into the target place The initial concentration of the solution had a marked effect on the particle size for operating conditions close to the mixture critical point An increase in the initial concentration of the polymer solution led to smaller particles sizes for both polymers In our case, an increase in the initial concentration of the solution led to higher supersaturation tending to decrease the particle size with a narrower distribution Thus, the first effect prevails under the operating conditions used in this work However, other authors have observed the opposite effect in other polymers’ precipitation:, i.e., a decrease in the solute concentration of polymer leading to smaller particle sizes and narrower particle size ranges [45] It is clear that not only the thermodynamics but also the hydrodynamics of the process must be taken in account In this case, an increase in the initial solute concentration can increase the time required to expand the liquid phase and to achieve supersaturation At higher solute concentrations, precipitation of the solute occurs earlier during the expansion process, resulting in increased time for crystal growth By operating in the supercritical region, pressure and temperature can be used to regulate the fluid density, which, in turn, regulates the solvent power of a supercritical fluid In this way, smaller particle sizes and narrower particle size distributions were produced at higher operating pressures for PLA This result can be explained by considering that an increase in pressure at constant temperature enhances the solvent power of supercritical CO2 towards the organic solvent; thus, the liquid solvent molecules are more strongly captured by CO2 and this reduces the possible interaction between the solvent and PLA [68] Temperature had the most marked influence on the both polymers’ particle size As example of this effect is shown in Fig 22.8 An increase in the operating temperature led to an increase in particle size A similar trend was found by Bakhbakhi 909 910 Supercritical Antisolvent Process as Green Alternative in Polymer Optimization et al [45]: An increase in the process temperature for the crystallization process resulted in a direct increase in the PLA mean particle size from 1.05 µm at 35°C to 8.71 µm at 40°C and, finally, to 47.3 µm at 50°C Figure 22.8 SEM images of SAS-processed PLA at different temperatures [53] However, the variation of particle size with pressure is more complex for Eudragit: First, the particle size increases with pressure, and it goes through a maximum at a pressure of about 150 bar and then decreases slightly (Fig 22.9) The cause of this behavior is that with higher pressures, the solubility of this acrylic copolymer in CO2 is higher, but the solubility in the organic solvent is lower Therefore, at higher pressures, the increase of the supersaturation in the solvent-rich region can balance the decrease in the CO2-rich region [31] Anyway, different trends are found in the literature about pressure effect in the way that the precipitation of other acrylic polymers using scCO2 antisolvent process seemed to be independent of pressure in the range of 80–120 bar at a fixed temperature of 40°C [43] Even as pressure increased, the mean particle size got smaller in other polymer processing [47, 67] Figure 22.9 SEM images of SAS processed Eudragit at different pressures [54] SAS Polymer Precipitation Process Not only thermodynamic parameters such as pressure and temperature but also hydrodynamic parameters such as nozzle diameter and liquid solution flow rate of both polymers were investigated using the SAS process In order to achieve successful precipitation of polymer nano- and microparticles from a single supercritical phase, the experimental conditions (pressure and temperature) should be far above the mixture critical point (MCP) of CO2 and solvent Anyway, the appropriate nozzle diameter and jet velocity should be used in order to ensure an atomization mode near to, or slightly above, this mixture critical point The jet breakup time should be higher than the time for the disappearance of the interface between the liquid and the fluid phase Theoretically, differences in nozzle diameter lead to different jet velocities In this way, smaller nozzle diameters result in higher jet velocities, which in turn lead to an increase in turbulence and the production of smaller particles [69, 70] It was demonstrated that nozzle diameter had a negligible effect on particle size and morphology of PLA in the complete miscibility region However, for Eudragit, smaller nozzle diameter led to smaller particle size and particle size distribution This can be explained by smaller nozzle diameters resulting in higher jet velocities, which in turn lead to an increase in turbulence and the production of smaller particles [69] The liquid solution flow rate was tuned between and mL/min in order to modify the degree of mixing of CO2 and the sample solution The variation of the liquid solution flow rate did not appreciably modify the particle size up to mL/min However, at mL/min the particle size increased but the morphology remained unaltered For Eudragit, liquid solution flow rate of and mL/min led to higher particle size and particle size distribution than the corresponding to mL/min experiment So, nozzle diameter of 100 µm and liquid solution flow rate of mL/min are recommended in order to obtain particles in the nanometer range In order to observe the possible modification and changes in crystallinity of both polymer by SAS process FTIR spectroscopy, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were carried out When processed, PLA and Eudragit exhibited the same bands as commercials although the intensities bands were lower; so no chemical alteration was produced For PLA, Younes and Cohn found two bands related to the crystalline and amorphous phases: The 911 912 Supercritical Antisolvent Process as Green Alternative in Polymer Optimization peak at 757 cm–1 can be assigned to the crystalline phase, while the peak at 870 cm–1 can be assigned to the amorphous phase [71] Thus, the crystalline phase was more prevalent in the commercial PLA than in the supercritical processed samples (Fig 22.10) Figure 22.10 FTIR of unprocessed and SAS processed PLA [53] This fact was corroborated by XRD The XRD patterns shown in Fig 22.11 indicate that there is a reduction in the degree of crystallinity in the SAS processed sample, a change that would make the polymer more flexible In the solid-state structure of amorphous polymers (glassy polymers) the chains are entangled in disordered coils, whereas crystalline polymer chains are packed and arranged in a regular structure The diffractogram of unprocessed polymers indicated amorphous and semicrystalline structure with a low degree of crystallinity, but after the SAS process, the amorphous structure was also more pronounced Mano et al found that the glass transition is shifted to lower temperatures on decreasing the crystalline polymer content [72] This change can be attributed to the very fast precipitation, which does not allow time for the organization of the solute morphology SAS Polymer Precipitation Process The thermal degradation of polymers was investigated by DSC In case of PLA, the melting point remained virtually unchanged after micronization by the SAS process but the glass transition temperature decreased from 72.50 to 63.81°C and this was accompanied by a decrease in the crystallinity [72] This remarkable depression in glass transition temperature is associated with increased mobility in the polymer chains, which allows for a faster relaxation and a more rapid crystallization of the polymers at any temperature between the glass transition and the degradation temperature [73] The glass transition temperature is an important factor for describing the physical properties of polymers By altering the glass transition temperature of drug or polymer molecules they can be maintained in amorphous solid form at room or body temperatures Improvement in handling characters, solubility, and storage of finished pharmaceutical dosage forms can be achieved by adjusting the glass transition temperature This temperature depends most of all on the type of polymer but also on its crystal forms, including plasticizers or other additives Figure 22.11 XRD pattern of unprocessed and SAS processed PLA (left) and Eudragit (right) [53, 54] The DSC thermograms of Eudragit are presented in Fig 22.12 as example Melting temperature around 200°C is associated to crystalline portion The SAS processed sample melting temperature went down slightly to 180°C due to the crystalline portion was decreased as it was shown by XRD analyses This thermal curve is also characterized by a broad endotherm peak around 72.90°C This peak corresponds to glass transition temperature Once 913 914 Supercritical Antisolvent Process as Green Alternative in Polymer Optimization polymer is processed by the SAS technique, the glass transition temperature goes down to 43.37°C acquiring more plastic behaviour The glass transition temperature of some polymers may be decreased after contact with supercritical fluid due to taking the place of CO2 for a very short time because of intermolecular interaction between the biodegradable polymers and dissolved supercritical fluid [74] As a result, PLA and Eudragit were plasticized under supercritical CO2, at the washing time step, to give a more flexible polymer that would be expected to exhibit plastic material behavior such as strength and toughness with good impact resistance [75] Figure 22.12 DSC diagrams of unprocessed and SAS processed Eudragit [54] 22.5 Conclusions Supercritical fluid processes is being explored as green alternative in polymer processing to improve the polymer properties, reduce cost, and extend the use for thermolabile active substance in the fields of cosmetics, food, and pharmaceuticals Particularly, SAS process have been used at our facilities to precipitate a nonbiodegradable polymer, ethyl cellulose, a biodegradable polymer, PLA, and a smart polymer with specific targeting area, Eudragit L100 Thermodynamics parameters such as the polymer References concentration, pressure, and temperature of the vessel and hydrodynamic parameters such as liquid solution and carbon dioxide flow rates and nozzle diameters, both of which could influence the final product features, were explored and optimized It was observed that generally an increase in the initial concentration of the polymer solution led to smaller particle size with a narrower distribution Temperature had the most marked influence on the both polymers particle size; hence, the higher the temperature, the higher particle the size However, the variation of the particle size with pressure is more complex and a different trend was observed for the polymers used Regarding hydrodynamic aspects, 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Structure Determination Results and Discussion Conclusion Cellulose: Structure and Property Relationships Michael Ioelovich 7.1 Introduction 7.2 Methods of Investigation of Supermolecular Structure