Handbook of sustainable polymers structure and chemistry

Compared with traditional synthetic polymer–based materials, sustainable polymer–based materials offer a number of advantages such as low-cost, specific mechanical properties, and ease o

Handbook of SUSTAINABLE POLYMERS

for the World Wind Power The Rise of Modern Wind Energy

Structure and Chemistry

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what I am today.

Vijay Kumar Thakur

2.2.1 Properties of Fibers from Different

Wood Species and Different Processes 202.2.1.1 Fiber properties of different

2.2.3.5 Shrinkage 402.3 Methods of Cellulose Fiber Modification for

Rascón-Chu Agustín, Díaz-Baca Jonathan A.,

Carvajal-Millán Elizabeth, López-Franco Yolanda,

and Lizardi-Mendoza Jaime

3.8.3 Pectins as Drug Controlled Delivery Systems 88

3.9.1.1 Pectin–protein interactions 903.9.1.2 Properties of complex composites 913.9.1.3 Fabrication of composite matrices 92

Mohamed Rashid Ahmed Haras, Mohamad Nasir Mohamad

Ibrahim, and Rohana Adnan

4.2.1 Oil Palm Industry 116

4.4.2.2 Graft copolymerization reaction 124

4.5 Application of LGC as a Drilling Mud Additive 132

4.5.2 The Ability of LGC as a Drilling Mud

4.5.2.1 Optimization of LGC dosages 1364.5.2.2 Comparison study between LGC

and commercial additives at high

5.2 Equal Channel Angular Pressing Technology 155

5.4 ECAP of Cellulose-Based Natural Polymers 162

5.4.1 Microcrystalline Cellulose 1625.4.2 Cellulose with Wheat Gluten as Additive 166

7.4.2 Sorption of Vapor of Organic Liquids 240

9.2 Depolymerization Properties of Poly(Lactic Acid) 2909.2.1 Thermal Degradation Behavior of PLA

9.2.2 Thermal Degradation Behavior of PLA

9.2.2.1 Diverse mechanisms of PLA

9.3.1.1 Estimation from single and

multiple constant heating

9.3.1.2 Estimation from molecular

9.3.3 Precise Kinetic Analysis of PHB

10.7.2 Biofiber-Reinforced PLA Composites 355

10.7.2.1 Effects of fiber surface

10.7.3 Biofiber-Reinforced PHB Composites 362

11 Novel Smart Chitosan-Grafted Alginate Microcapsules pH-Sensitive Hydrogelfor Oral Protein Delivery:

11.2.2.1 Preparation of BSA loaded

11.2.2.2 Preparation of BSA loaded

11.2.2.3 Materials characterization 38911.2.2.4 BSA release experiments 390

12.2 Nature and Physical Properties of Reactants 418

12.2.2.1 Non-sulfated polysaccharides 41912.2.2.2 Sulfated polysaccharides 420

13.3 The Use of Agrowaste and the Production of

14.4 Preparation of CNF/Synthetic Polymer

Nanocomposite Materials by Surface-Initiated

15 Chitosan–Starch Ecocomposites: Sustainable Biopolymer

Cynthia Graciela Flores-Hernández,

Ana Laura Martínez-Hernández, and Carlos Velasco-Santos

15.3.2 Chitosan–Starch Films Reinforced

15.3.3 Processing Strategies for

Umile Gianfranco Spizzirri, Manuela Curcio, Giuseppe Cirillo,

Tania Spataro, Nevio Picci, and Francesca Iemma

17.8.2 Blends of Poly(d,l) Lactide Family 648

17.8.4 Poly(Vinyl Alcohol) and

17.9.5 Biodegradable Polymeric Nanoparticles

17.9.6 Biodistribution: Characteristics of

17.10 CMC Hydrogel Loaded with Silver Nanoparticles

17.15 Carrier of DNA: Nanospheres or Nanocapsules 65917.16 Bio-Based Packaging Materials by Chitosan

Nanoparticles Embedded with Eugenol for

17.17 Poly(Malic Acid) Biologically Mediated

Nanoparticle for Drug Delivery in

17.17.2 Features of Poly(Malic Acid)

17.18 Infrared Fluorescent Nanoparticles for Bone

Malignancy by Biodegradable Bisphosphonate

17.18.1 Synthesis of Biodegradable and

Non-Biodegradable Vinylic Monomers 66217.19 PLGA Nanoparticles under Treatment of

17.19.1 Complexity of Cancer Microenvironment 663

17.19.3 Strategies with Cancer Immunotherapy 663

17.21.5 Shape-Memory Effect by Specific

17.22 Ecological Applications: Processing of

Shamsher S Kanwar, Surabhi Mehra, Ram Baskarn,

and Ashok Kumar

18.5 Enzyme Immobilization and Entrapment 70418.6 Applications in Enzyme Technology and

Takaomi Kobayashi, Karla Tovar–Carrillo, and Motohiro Tagaya

19.1 Introduction: Bagasse Regeneration Process and

Approach for Tissue-Compatible Hydrogels 717

19.2.2 Purification Process of Agave Bagasse

19.2.3 Preparation of Cellulose Hydrogel Film

19.3 Unique Nature of Cellulose Hydrogel Films 72419.3.1 Properties of the Films Treated on

19.3.2 Effect of LiCl Concentration on

19.3.3 Dissolution of Different Solvent for

19.4 Tissue Regeneration on Cellulose Hydrogel

19.4.1 Evaluation of Cytotoxic Property 72819.4.2 Fibroblast Adhesion on Agave

19.4.3 Several Hydrogel Films Prepared

20 Smart Polymers in Targeted Drug Delivery 737

Sushama Talegaonkar, Lalit M Negi, Harshita Sharma,

and Sobiya Zafar

20.2 Classification 73920.2.1 Internal Stimuli-Responsive Polymers 739

20.2.1.1 Temperature-responsive

20.2.1.3 Enzyme-responsive polymers 76720.2.1.4 Redox-responsive polymers 77420.2.2 External Stimuli-Responsive Polymers 781

20.2.2.1 Photo-responsive polymers 78120.2.2.2 Magnetic-responsive polymers 78820.2.2.3 Ultrasound-responsive

21.3.2 Polymers Directly Produced by

21.3.3 Polymers Synthetized from Biobased

21.3.4 Polymers Synthetized Directly from

Antonio Montes, María Dolores Gordillo, Clara Pereyra,

and Enrique José Martínez de la Ossa

22.3 Supercritical Fluid Processes and Polymers 899

Synthetic polymers and their materials have been used frequently

as attractive alternatives to conventional materials for a number

of applications Some of the advantages of these materials are resistance to corrosion, acids, and fire; higher fatigue strength, impact energy, and absorption capacity; longer service life; lower life-cycle costs; and non-conductivity However, most synthetic polymer–based materials suffer from a number of drawbacks such

as non-biodegradability, non-recyclability, and non-environmental friendliness Compared with traditional synthetic polymer–based materials, sustainable polymer–based materials offer a number of advantages such as low-cost, specific mechanical properties, and ease of handling Furthermore, owing to the increasing environment and sustainability concerns, materials industries worldwide are undergoing a revolutionary shift to developing environmentally sustainable materials Natural polymers provide renewable resources, and applications of the natural polymer–based materials can also reduce the waste in the environment owing to their biodegradable nature One of the advantages of these materials is that these materials do not disrupt the established steady-state equilibrium of the environment

Compared with the traditional synthetic polymer–based materials, the use of biorenewable polymers for a number of applications ranging from biomedical to defense is increasing rapidly Indeed, biorenewable polymer–based materials have been used

by the people of earlier civilizations to meet their material needs Diversity of materials derived from different natural resources such as natural fibers, wood, animal skin, wool, and silk has played

a greater role in the early civilization These natural polymer–based materials are of high importance even in the modern world as their feedstocks are renewable Furthermore, natural polymer–based materials can be composted or recycled at the end of their life cycle Different research efforts all around the globe are

continuing to improve the existing properties of these polymers Researchers are collectively focusing their efforts to use the inherent advantages of sustainable polymers for their targeted applications Scientists in collaborations with industries are extensively developing new classes of sustainable materials of renewable nature Different kinds of sustainable materials can be obtained from different biorenewable polymers as well as some genetically modified organisms This book is solely focused on sustainable polymers and deals with the different structural and chemical aspects of these materials Several critical issues and suggestions for future work are comprehensively discussed in this book with the hope that the book will provide a deep insight into the state

of the art of sustainable polymers We would like to thank the publisher for the invaluable help in the organization of the editing process Finally, we would like to thank our parents for their continuous encouragement and support

Vijay Kumar Thakur Manju Kumari Thakur

Sustainable Polymers: A Perspective to the Future

1.1 Introduction

During the past few decades, synthetic polymers and their materials have been used frequently as attractive alternatives to conventional materials for a number of applications (Thakur et al., 2013c; Thakur et al., 2014) Some of the advantages of these materials include higher strength; resistance to corrosion, acid resistance, higher fatigue strength, impact energy, absorption capacity; better fire resistance, acids resistance, longer service life, lower life-cycle costs; non-conductivity and non-toxicity to name a few (Dittenber and GangaRao, 2012; Thakur et al., 2013) However, most of the synthetic polymer-based materials suffer from a number of drawbacks such as non-biodegradability, non-recyclable, and non-environment friendliness (Thakur et al., 2013c) Compared to the traditional synthetic polymer-based materials,

Vijay Kumar Thakur a and Manju Kumari Thakur b

Washington State University, USA

Himachal Pradesh University, Shimla, Himachal Pradesh 171005, India

shandilyamn@gmail.com, vijayisu@hotmail.com

Handbook of Sustainable Polymers: Structure and Chemistry

Edited by Vijay Kumar Thakur and Manju Kumari Thakur

Copyright © 2016 Pan Stanford Publishing Pte Ltd.

ISBN 978-981-4613-55-2 (Hardcover), 978-981-4613-56-9 (eBook)

www.panstanford.com

sustainable polymer-based materials offers a number of advantages such as their low-cost, specific mechanical properties, easier to handle to name a few (Thakur et al., 2013a) These materials also require only around 20–40% of the production energy Sustainable polymers and materials refer to the materials that can be produced

in a desired amount without depleting the non-renewable resources One of the advantages of these materials is that these materials

do not disrupt the established steady-state equilibrium of the environment (Thakur et al., 2013a) All the biorenewable polymer-based materials and some of the highly recyclable materials comes under the domain of sustainable materials (Thakur et al., 2013a) This book is solely focused on the sustainable polymers and deals with the different structural and chemical aspects of these materials Therefore, in the following section, we will be focusing only on some fundamental aspects of sustainable polymers discussed in detail in this book

Compared to the traditional synthetic polymer-based materials, the use of biorenewable polymers for a number of applications ranging from biomedical to defense is increasing rapidly Indeed the biorenewable polymer-based materials have been used by the people of earlier civilizations to meet their material needs (Singha and Thakur, 2012) A diversity of materials derived from different natural resources such as from natural fibers, wood, animal skin, wool, and silk have played a greater role in early civilization (Singha and Thakur, 2012) These natural polymer-based materials are of high importance even in the modern world

as their feedstocks are renewable Furthermore, the natural polymer-based materials can be composted or recycled at the end

of their life cycle (Thakur et al., 2012a) Different research efforts all around the globe are continuing to improve the existing properties

of these polymers Researchers are collectively focusing their efforts to use the inherent advantages of these polymers for their targeted applications (Thakur et al., 2012b) Scientists in collaborations with industries are extensively developing new classes of sustainable materials of renewable nature Different kinds of sustainable materials can be obtained from different biorenewable polymers as well as some genetically modified organism (Thakur and Thakur, 2014)

Rising environmental awareness has resulted in the use of environment-friendly materials for a number of applications

(Thakur et al., 2014) Especially the use of sustainable materials is ing unceasingly In case of biopolymer-based materials, these materi-als are generally divided into three different types such as (1) those directly developed from biomass (2) those procured using chemi-cal synthesis from biorenewable monomers (3) those produced directly by natural or genetically modified organisms Figure 1.1 summarizes the general classification of biorenewable polymers.

ris-Figure 1.1 Biorenewable polymers procured from different natural

resources (Singha and Thakur, 2012)

Among different biorenewable polymers, the most common sources of these polymers are agricultural and marine sources (Singha and Thakur, 2012) The inherent properties of these poly-mers that make them a material of future are their biodegradability and biocompatibility Due to their advantages, these polymers are considered ideal candidates for multifunctional applications in agriculture, biomedical, textiles, automotive, electronic, ophthal-mology, medicine, paper coatings, etc The most important role in controlling the overall properties of these polymers is played by their chemical structure and morphology (Singha and Thakur, 2012) These two parameters influence their properties and biological functions (Singha and Thakur, 2012) It has been well documented

in the existing literate that same polymer can play different roles depending on its chemical structure (Singha and Thakur, 2012) Below are some of the most commonly used biopolymers being explored for a number of applications

1. Natural Cellulose Fibers

Natural fibers are the most common biorenewable polymers available in abundance all around the globe Some of the commonly occurring natural fibers all around the globe include flax, hemp, baggase, jute, pine needles, pineapple leaf, sisal, grewia optiva, hibiscus sabdariffa (Santos et al., 2013) Figure 1.2 shows the extraction of pineapple leaf fiber from its plant

(c) (d)

Figure 1. Photographs of (a) the pineapple cultivation, (b) untreated

pineapple leaves, (c) ground pineapple leaves, and (d) treated pineapple leaves Reprinted with permission from Santos

et al (2013) Copyright 2013 Elsevier.

Each of these natural cellulosic fibers is composed of three components, namely, cellulose, hemicellulose, and lignin along with some impurities (Frollini et al., 2013) Each of these components plays an important role in determining the overall properties of the fibers as well as determines the strength of the fibers Figures 1.3a–d shows the structure of cellulose, hemicellulose, lignin, and cell wall

Figure 1.a Chemical structure of cellulose Reprinted with permission

from Akil et al (2011) Copyright 2011 Elsevier.

Figure 1.b Structures of hemicelluloses Reprinted with permission from

Thakur and Thakur (2014) Copyright 2014 Elsevier.

Figure 1.c Chemical structure of a softwood lignin Reprinted with

permission from Fernandes et al (2013) Copyright 2013 Elsevier.

Figure 1.d Schematic picture of cell wall of the natural plants Reprinted

with permission from Thakur and Thakur (2014) Copyright

2014 Elsevier.

Figure 1.e Microstructure of wood fiber cell wall: P primary cell wall

layer, S1, S2, and S3 are the inner, middle, and outer layers of the secondary wall, respectively Reprinted with permission from Abdul Khalil et al (2012) Copyright 2012 Elsevier.Among the three essential components of natural fibers, cellulose is a non-branched macromolecule and contains chain

of variable length of 1-4 linked b-d-anhydroglucopyranose units (Thakur and Thakur, 2014) It has been reported that the length

of chain in cellulose fibers depends on the source of cellulose from which it is procured Hemicellulose, on the other hand, is composed

of a group of polysaccharides with the exclusion of pectin and has a branched structure It has been reported that hemicellulose remains associated with cellulose even after the removal of lignin

(Thakur and Thakur, 2014) Among cellulose, hemicellulose, and lignin, lignin is a highly branched polymer It mainly consists of phenyl propane units (Thakur and Thakur, 2014) These units are organized in a three-dimensional structure These units are linked together through various types of carbon–carbon and ether bonds

as opposed to the chains in cellulose and hemicellulose (Thakur and Thakur, 2014) Figure 1.3d,e shows the schematic structure

of natural plant cell wall It is clear from the figure that the cell wall primarily consist of a hollow tube with four different layers commonly known as primary cell wall, secondary cell walls, and

a lumen (Thakur and Thakur, 2014)

Table 1.1 Factors affecting fiber quality at various stages of natural fiber

production

Plant growth Species of plant

Crop cultivation Crop location Fiber location in plant Local climate

Harvesting stage Fiber ripeness, which effects:

– Cell wall thickness – Coarseness of fibers – Adherence between fibers and surrounding structure Fiber extraction

stage Decortication processType of retting method

Supply stage Transportation conditions

Storage conditions Age of fiber

Source: Reprinted with permission from Thakur and Thakur (2014) Copyright 2014

Elsevier.

It has been well documented in the existing literature that during the production of fibers from different resources, numerous factors affect the overall quality of the natural fibers depending

on the condition (Thakur and Thakur, 2014) Table 1.1 shows the factors that affect the overall quality of the fibers, and Table 1.2

shows the chemical composition of some selected natural cellulosic fibers (Thakur and Thakur, 2014) It has been reported in the literature that similar to bone, natural cellulosic materials also exhibit pores These pores are used for the transportation of nutrients Both bone and wood have been found to present nearly the same hierarchical structure from the nano- to the macro-scale

as shown in Fig 1.4 (Fernandes et al., 2013) Figures 1.5a,b also depicts some of the constituents and SEM images of the natural cellulosic fibers

Table 1. Chemical composition of some typical cellulose-containing

materials

Type of

biofiber

Composition (%) Source Cellulose Hemicellulose Lignin Extract

Figure 1. Schematic representation of hierarchical structure of

lignocellulosic materials and bone from nano to the scale Reprinted with permission from Fernandes et al (2013) Copyright 2013 Elsevier.

macro-Figure 1.a Fiber components Reprinted with permission from Frollini

et al (2013) Copyright 2013 Elsevier

(a) (b)

Figure 1.b Fiber surfaces SEM micrographs of (a) sugarcane bagasse;

(b) coconut; (c) curaua; (d) sisal Reprinted with permission from Frollini et al (2013) Copyright 2013 Elsevier.

These fibers are frequently used in a number of applications, especially in the field of polymer composites Most common advantages of these natural fibers include biodegradable, light weight, high specific modulus, non-toxic, environment friendliness, and ease of processing and absorbing CO2 during their growth (Kabir et al., 2012) These fibers, in spite of their advantages, suffer from a few drawbacks such as sensitivity to moisture absorption and low chemical resistance (Thakur and Thakur, 2014) So these need to be modified physically and chemically Some of the common techniques used to improve the surface properties of these polymers include grafting and chemical functionalization (e.g., alkaline treatment, silane treatment, acetylation treatment, benzoylation treatment, peroxide treatment, maleated coupling agents, sodium chlorite treatment, isocyanate treatment, stearic acid treatment, permanganate treatment, triazine treatment, etc.) (Kabir et al., 2012; Thakur and Thakur, 2014) Compared to the traditional synthetic fibers, these natural fibers are much cheaper and easily available Figure 1.6a,b shows the comparison between the glass and natural fibers (Dittenber and GangaRao, 2012)

(b)

Figure 1. (a) Cost per weight and (b) cost per unit length comparison

between glass and natural fibers Reprinted with permission from Dittenber and GangaRao (2012) Copyright 2012 Elsevier.

Figure 1. Life cycle of bio-composites Reprinted with permission from

(Akil et al., 2011) Copyright 2011 Elsevier.