Biodegradable Polymers: Concepts and Applications

354 Pages·2023·7.743 MB·English

by  Margarita del Rosario Salazar Sánchez, José Fernando Solanilla Duque, Aidé Sáenz Galindo, Raúl Rodríguez Herrera

Biodegradable Polymers
Concepts and Applications
Editors
Margarita del Rosario Salazar Sánchez
Departamento de Ciencias Agroindustriales

Facultad de Ingenierías y Tecnológicas

Universidad Popular del Cesar

Cesar, Colombia

José Fernando Solanilla Duque
Departamento de Agroindustria

Facultad de Ciencias Agrarias

Universidad del Cauca

Popayán, Colombia

Aidé Sáenz Galindo
Facultad de Ciencias Química

Universidad Autónoma de Coahuila

Saltillo, México

Raúl Rodríguez Herrera
Universidad Autónoma de Coahuila

Saltillo, México

A SCIENCE PUBLISHERS BOOK
Cover illustration reproduced by kind courtesy of Margarita del Rosario Salazar Sánchez.
First edition published 2023
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© 2023 Margarita del Rosario Salazar Sánchez, José Fernando Solanilla Duque, Aidé Sáenz Galindo and Raúl
Rodríguez Herrera
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Library of Congress Cataloging‑in‑Publication Data (applied for)
ISBN: 978-1-032-13714-8 (hbk)
ISBN: 978-1-032-13715-5 (pbk)
ISBN: 978-1-003-23053-3 (ebk)
DOI: 10.1201/9781003230533
Typeset in Times New Roman
by Radiant Productions
Preface

As a consequence of the negative impact of synthetic polymers on the environment, not only for
the present generation but also for future generations, the need has arisen to develop biodegradable
polymers that not only meet most of the quality standards for the manufacture of products but also
have a degradation period much shorter than that of synthetic polymers. This book appears as a
collaborative project between different institutions of higher education and research in order to
bring together the different topics related to the production, application and final destination of
biodegradable polymers, and their impact on modern life and on future generations.
The book of biodegradable polymer science reveals the basic concepts of biodegradable
polymer science, describing the techniques, standards and analysis to be performed to characterize
biodegradable polymeric materials, highlighting that it is important to further develop and/or innovate
processes considering the environment. Pointing to this, this book focuses on the engineering of
biopolymers in food processing and explores the processing technology associated with biopolymer
applications. The difference between a normal book on biodegradable polymers and the present book
is that in our version, there are some very interesting chapters that are framed on the rheological and
structural analysis, in addition to the applications in different areas of knowledge such as: health,
agriculture and technology.
The present book will be useful for the biodegradable polymer’s industry because it covers from
films to composites, as well as in academia and research including framing processes of analysis
and technology which could be used to improve biodegradable polymer production, where the
reader will find different tools to become familiar with biopolymers analysis and implementation
of these analyses. The contribution of this book would complement the themes developed by a
reference book on biodegradable polymer bases because this book refers to treatment topics among
which are Compounding and Additives, Powdering, Chemical Treatment, Surface Treatment,
Adhesive Compositions, Biopolymer Engineering in Food Processing and Biodegradation, other
product developments from these biopolymers are also covered. All applications are shown from
a sustainability and sustainability approach, it is important to highlight that biodegradability has a
great burden when it involves substituting, modifying and/or designing existing processes in harmful
and polluting processes. The book concludes with a reflection on the development of biodegradable
polymers in different areas of knowledge and trends.
Contents

Preface iii
Introduction vi
1. Biodegradation of Polymers 1
Sarai Agustín Salazar, Sabu Abdulhameed and Margarita del Rosario Salazar Sánchez
2. Use of Renewable Source in Biodegradable Polymer 13
J.J. Cedillo‑Portillo, J.D. Flores‑Valdes, W.Y. Villastrigo‑López, D.W. González‑Martínez,
A.O. Castañeda‑Facio, S.C. Esparza‑Gonzalez, R.I. Narro‑Céspedes and A. Sáenz‑ Galindo
3. Plastics Technology 32
Marlene Lariza Andrade‑Guel, Alma Berenice Jasso‑Salcedo, Diana Iris Medellín‑Banda,
Marco Antonio De Jesus‑Tellez and Christian Javier Cabello‑Alvarado
4. Analysis and Testing of Biopolymers 55
María C. García‑Castañeda, Kassandra T. Ávila‑Alvarez, Marco A. García‑Lobato,

Anna Ilyina and Rodolfo Ramos‑González

5. Structure and Morphology of Biodegradable Polymers 64
Felipe Avalos Belmontes, Francisco J. González, Mónica Esmeralda Contreras Camacho,
Aidé Sáenz‑Galindo and Rodrigo Ortega Toro
6. Rheology Properties of Biodegradable Polymers 80
Juan Pablo Castañeda Niño, José Herminsul Mina Hernandez,

Heidi Andrea Fonseca Florido, Leticia Melo López,

Margarita del Rosario Salazar Sánchez and Jose Fernando Solanilla Duque

7. Structural Analysis of Polymers and Composite Materials 99
Juan Pablo Castañeda Niño, José Herminsul Mina Hernandez, Alex Valadez González
and Jose Fernando Solanilla Duque
8. Films 112
Karla C. Córdova‑Cisneros, Paola F. Vera‑García, Karina G. Espinosa‑Cavazos,

Omar A. Martínez‑Anguiano, Aidé Sáenz‑Galindo and Adali O. Castañeda‑Facio

9. Composites and Novel Applications in the Biomedical Field 129
Claudia Gabriela Cuellar Gaona, Rosa Idalia Narro Céspedes, Ricardo Reyna, Martínez,
Víctor Adán Cepeda Tovar, Karina Reyes Acosta and Aidé Sáenz Galindo
10. Green Materials in the Packaging: Biodegradable Foams 148
Sindhu Thalappan Manikkoth, Deepthi Panoth, Kunnambeth M. Thulasi, Fabeena Jahan,
Anjali Paravannoor and Baiju Kizhakkekilikoodayil Vijayan
11. Biodegradable Foams: Processes and Applications 160
Lorena Farías‑Cepeda, Lucero Rosales Marines, Anilú Rubio Rios,

Victor A. Cepeda Tovar, Karina Y. Reyes Acosta and Bertha T. Pérez‑Martínez
Contents v

12. Thermo-Shrinkable Biodegradable Polymers 177

Reyes‑Acosta Yadira Karina, Farias‑Cepeda Lorena, Rubio‑Ríos Anilú,

Rosales‑Morales Lucero, Reyna‑Martínez Ricardo, Alonso‑Montemayor Francisco Javier

and Cepeda‑Tovar Víctor Adán

13. Applications of Biodegradable Polymers in Food Industry 189

Jose Fernando Solanilla‑Duque, Diego Fernando Roa‑Acosta, Luis Daniel Daza,

Darwin Carranza‑Saavedra, Henry Alexander Váquiro, Juan Pablo Quintero‑Cerón,

Maria Julia Spotti and Carlos Carrara

14. Health Applications of Biodegradable Polymers 207

Sandra Cecilia Esparza González, Aide Saenz Galindo, Raúl Rodriguez Herrera,

Claudia Magdalena López Badillo, Lissethe Palomo‑Ligas, Isai Medina Fernandez and

Victor de Jesús Suarez Valencia

15. Natural Polymers: Applications in the Health Field 218

Carneiro‑da‑Cunha, M. G., Granja, R. C. B., Souza, A. A., Melo, E. C. C., Oliveira, W. F.
and Correia, M. T. S.
16. Bioplastics: Challenges and Opportunities 229

Lily Marcela Palacios, Germán Antonio Arboleda Muñoz, Héctor Samuel Villada Castillo
and Hugo Portela Guarín
17. Tendencies and Applications in Biodegradable Polymers 243

Lucía F. Cano Salazar, Denis A. Cabrera Munguía, Tirso E. Flores Guía,
Jesús A. Claudio Rizo, Martín Caldera Villalobos and Nayvi Y. Nava Cruz
18. Tendencies in Development of Biodegradable Polymers 260

Lluvia Itzel López‑López
19. Assessment of Biodegradability in Polymers: Mechanisms and Analytical Methods 272

Francisco J. González, Francisco J. Rivera‑Gálvez, Felipe Avalos Belmontes and
Mario Hoyos
20. Biodegradable Packaging: Colombian Coffee Industry 289

Germán Antonio Arboleda Muñoz, Lily Marcela Palacios, Hugo Portela Guarín and
Héctor Samuel Villada Castillo
21. Agriculture Applications of Biodegradable Polymers 300

Rocio Yaneli Aguirre‑Loredo, Lluvia de Abril Alexandra Soriano Melgar, Luis Valencia,
Gonzalo Ramírez García and Alma Berenice Jasso‑Salcedo
22. Insight on Polymeric Hydrogel Networks: A Sustainable Tool for the Isolation 320

of Enzymes and Bioremediation

Bárbara Bosio, Paola Camiscia, Guillermo Picó and Nadia Woitovich Valetti

Index 337

Editors Biography 339
Introduction
Zainul Akmar Zakaria,1 Siti Hajjar Che Man,1 Rocio Castillo‑Godina2
and Raul Rodriguez‑Herrera2
Biopolymers are produced by living organisms and should be differentiated for its term synthetic
biodegradable polymers. The monomer units of most biopolymers usually consist of recurring
molecules of either nuclei acid of nucleotides (deoxyribonucleic acid, DNA and ribonucleic acid,
RNA), amino acid proteins (collagen, gelatin, gluten) or saccharides derived from sugars such as
cellulose, chitosan, chitin (Samrot et al., 2020). Increasing depletion of petroleum-based resources
to produce various types of polymers as well as its associated non-biodegradability features,
has become the major driving force in the continuous development in the area of biopolymers
production, processing and applications. Biopolymer offers an interesting and viable solution for
this problem based on its biodegradability features. Notably, some weaknesses such as high cost,
limited rate of production and poor mechanical properties have been identified as focus for further
investigation in this area. Biopolymers are comprehensively segregated into two principle groups
namely biodegradable and non-biodegradable (Rai et al., 2021). They can also be classified as
elastomers, thermosets and thermoplastics according to their physical and chemical changes when
stressed in different thermal conditions (George et al., 2020). Other researchers have classified
biopolymers according to its various forms of either composites, blends or laminates. Some
examples for commercially-produced biopolymers include polyesters (polyhydroxybutyrate,
PHB) and (polybutylene succinate, PBS), bio-polyolefins, Bio-PE (polyethylene), bio-polyamides,
Bio-PA (homopolyamides - Bio-PA 6, Bio-PA 11) and biopolyurethanes, Bio-PUR.
Biopolymers have been established and gained significant interest in various applications such
as biomedical, nanomaterials, food industry as well as water treatment. The ability of this polymer
to be tailored with other materials to suit certain properties made them more attractive and feasible.
In biomedical applications (Moohan et al., 2020), biopolymers such as starch, cellulose, chitosan,
polylactic acid (PLA) (Ghalia and Dahman, 2017) and Poly (Glycolide Acid) (PGA) have been
extensively used for tissue engineering, pharmaceutical carriers and medical devices. These polymers
are known for their advantageous features that include cytocompatibility and the ability to degrade
in the body without releasing harmful substances. Tyler et al. (2019) reviewed the applications of
PLA and its copolymers as nanoparticle drug carriers, such as liposomes, polymeric nanoparticles,
dendrimers and micelles. The ability of PLA to be moldable, allowing its applications to take on
numerous shapes, i.e., scaffolds, sutures, micelle, etc., to suit such applications. Other than PLA,
biopolymers such as gelatin and hydroxyapatite (HA) has been long used as artificial scaffolds, due
to their compatibility to the natural bone tissue (Hajinasab et al., 2018; Szcześ et al., 2017). Despite
1 School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310 UTM Johor
Bahru, Johor, Malaysia.
2 Autonomous University of Coahuila, School of Chemistry, Blvd. V. Carranza and J. Cardenas s/n, Col. Republica Ote.
Saltillo Coahuila 25280. México.
* Corresponding author: [email protected]
Introduction vii
their advantages, there are several limitations that restrict their use for these particular applications
due to the lack of mechanical strength. To date numerous studies have been reported to improve the
issue with the property’s instability of this biopolymers (Hamad et al., 2015; Reddy et al., 2015).
Recently, biopolymers are preferred to be used in food packaging coating to replace the
traditional non-degradable materials such as polypropylene, polyethylene, etc. The demand for
higher shelf life as well as better packaging quality have led to the increased interest in this area.
Biopolymers such as starch, polyhydroxyalkanoates (PHA), polyhydroxybutyrates (PHB), PLA and
so on, are among the commercially viable materials in food packaging, which can be processed
via conventional equipment. Barrier properties is an extremely important characteristic especially
for biobased food packaging materials. Biopolymers are known as hydrophilic materials with
inadequate moisture resistance. Thus, various improvements have been reported to enhance the
barrier properties as well as the mechanical properties. The development of coatings from natural
polymers for food packaging have received significant interest to overcome the issue. Various
polysaccharides and protein-based compounds have been investigated for food packaging coating
which shown good grease, good affinity to the packaging substrate as well as a positive effect on
mechanical properties (Nechita et al., 2020). Chemical and physical crosslinking such as grafting
and coating have been reported to improve the compatibility of the coating and substrate (Reddy
et al., 2015). The incorporation of nanofillers into biopolymers matrices not only to enhance the
mechanical and barrier properties but also to impart other attractive properties such as antimicrobial
agent and biosensor (Othman, 2014; Qamar et al., 2020).
Preparation of nanomaterials derived from cellulose (CNs) have recently gained significant
interest, due to their excellent inherent and physical properties. In addition, CNs may serve as an
inexpensive, renewable and biodegradable in comparison to its counterpart carbon nanotubes (CNTs).
It was reported that CNs exhibited a greater axial elastic modulus than Kevlar and its mechanical
properties are within the range of other reinforcement materials. The presence of reactive surface of
–OH side groups in the structure of CNs enables the grafting of chemical species to achieve surface
functionalization which allows the tailoring of particle surface chemistry to facilitate self-assembly
(Moon et al., 2011). To date, the potential of CNs have been recognized in various fields, i.e., paper
and packaging, automotive, medical, construction, personal care, textile industries as well as waste
water treatment (Carpenter et al., 2015; Mohan et al., 2020; Tayeb et al., 2018).
In other applications, biopolymers have been incorporated in the fabrication of lithium-ion
battery separators due to the excellent properties particularly low cost, high thermal stability,
excellent mechanical properties, non-toxic, light-weight and excellent wettability to the electrolyte
(Xu et al., 2014; Zhang et al., 2019). Whereas in biosensor application, biopolymer is a great
material to be used as it can act as good immobilization matrix for entrapping biorecognition units
such as enzymes, whole cells and others and provide good adhesion of the composite to electrode
for carrying out sensing measurements.
Next the most important facts of the book chapters will be mentioned. In Chapter 3 on the
science of biodegradable polymers, it is emphasized that synthetic polymers in general meet many
needs of the human population, which is why they are materials of mass consumption, however,
characteristics such as: high resistance to corrosion, water and bacterial decomposition makes
them difficult to eliminate, and consequently, a serious environmental problem that lasts for years
(Valero-Valdivieso et al., 2013). On the other hand, there has been a demand for products that
replace petroleum-derived plastics with alternatives based on renewable resources and above
all biodegradable. This focuses an approach of multiple scientific disciplines and the so-called
science of biodegradable polymers arises. Biodegradable polymers are those that have the ability
to decompose in the presence of enzymes produced by microorganisms such as: bacteria, fungi and
algae. It is necessary to differentiate between degradable, which refers to decomposition due to
chemical or physical changes, while biodegradable is due to degradation by biological mechanisms
(Niaounakis, 2013; Karamanliouglu et al., 2017).
viii Biodegradable Polymers: Concepts and Applications
The latest trends in polymer production include the use of renewable sources (Chapter 4) instead
of traditional polymers based on fossil sources, responsible for CO emissions into the atmosphere
2
and which also generate non-biodegradable waste, taking years for its decomposition, which
therefore represents an environmental problem (Peplow, 2016; Llevot et al., 2016). Biodegradable
polymers can be produced by biological systems (microorganisms, plants and animals) or they can
be synthesized from biological raw materials (for example, corn, sugar, starch, etc.), also known
as bio-based (Gómez and Yory, 2018). In general, the production of these biopolymers includes
synthetic polymers obtained from renewable resources, such as: polylactic acid (PLA); biopolymers
produced by microorganisms such as polyhydroxyalkanoate (PHA) and natural biopolymers such as
starch or proteins (Rudin and Choi, 2013).
Biodegradable polymers can be classified as follows:
• Polymers extracted or removed directly from biomass: polysaccharides such as starch and
cellulose. Proteins like casein, keratin and collagen.
• Polymers produced by classical chemical synthesis using biological monomers from renewable
sources.
• Polymers produced by microorganisms, native or genetically modified producing bacteria.
In Chapter 5, the authors focus on plastics technology, specifically those of biological origin:
PHAs and polylactic acid (PLA). PHAs are also called “double green polymers.” PLA is a natural
monomer produced by fermentative ways from elements rich in sugars, cellulose and starch.
Bioplastics have physicochemical and thermoplastic properties equal to those of polymers made
from oil, but once deposited under favorable conditions, they biodegrade (Díaz del Castillo, 2012).
Polymerization is the process in which small molecules of a single unit (monomers) or of a few units
(oligomers) are chemically united to create bigger molecules, in which the atoms are strongly linked
by a covalent bond (Díaz del Castillo, 2012). Currently, enzymatic polymerization represents a
great approach to functionalizing polymers and biopolymers and preventing the generation of waste
through the use of catalytic processes with high selectivity, as well as preventing or limiting the use
of dangerous organic reagents (Peponi et al., 2015).
The technological methods of manufacturing plastics are determined by their rheological
properties and will depend on whether the material in question is thermoplastic or thermoset.
Some of these methods are: injection molding, blow molding, rotational molding, blow processing
methods, calendaring, casting, coatings, extrusion, film techniques, foam forming, lamination and
low-pressure molding, filling techniques, plasticizers and other additives, an example of the latter
such as antioxidants and colorants (Billmeyer, 2020).
Polymers obtained from both oil and renewable natural resources need to be analyzed using
different methodologies, which are discussed in Chapter 6, within these techniques are: Analytical
methods in which the process used in polymers is not different from the techniques used in low
molecular weight organic compounds. The physical analysis of polymers consists of different
techniques: mass spectrometry and gas chromatography, infrared spectroscopy, in which the
emission and absorption spectra of the molecules are determined, X-ray diffraction analysis, nuclear
magnetic resonance spectroscopy and electrical spin, thermal analysis, which includes experimental
methods of calorimetry, differential thermal analysis, microscopy and physical tests that include
mechanical properties, fatigue tests, thermal properties, optical properties, electrical properties and
chemical properties (Billmeyer, 2020).
The structure of polymers is covered in Chapter 7, which depends on the shape of the
chains. Based on the structure, polymers can be classified as linear, branched or cross-linked
(López-Carrasquero, 2004). Linear polymers are those in which the monomeric units are linked side
by side in a single direction. Under certain conditions or with certain types of monomers, polymers
with another type of architecture can be obtained which are characterized by having branches that are
generated from the main chain, this characteristic has significant effects on many physical properties
Introduction ix
of the polymer, for example, in decreasing crystallinity. Branched polymers cannot easily fit into a
crystal lattice as linear polymers do. On the other hand, branched polymers are much less soluble
than their linear counterparts and cross-linked polymers are insoluble materials. Crosslinking can
occur during the polymerization process or later through various chemical reactions. Crosslinking
is used to impart good elastic properties in some elastomers, as well as to provide rigidity and
dimensional stability to some materials called thermoplastics.
Biopolymers have macromolecules (proteins, carbohydrates, etc.), that generate dispersions that
have certain rheological behaviors (Zambrano-Herrera, 2020). Rheology studies the fundamental
and practical knowledge of the deformation or flow of matter (Hernández, 2014). Based on the
above, Chapter 8 discusses the rheological properties of biopolymers. This branch of physics allows
the characterization of flow patterns during processing, which facilitates handling and operating
conditions, in addition to the properties of the final product (Zambrano-Herrera, 2020).
One of the most common forms of bioplastics is in the form of thin sheets obtained from
blowing films. In this procedure, a thin-walled tube is extruded and then expanded by increasing
the internal pressure of the tube (Mendoza and Velilla, 2011). In Chapter 9, the authors report the
research on thin films and mixtures to obtain biodegradable polymers. In this regard, starch is
widely used, given its availability and low cost. Starch is used as a thermoplastic in the production
of biodegradable plastics (Funke, 1998). During its production, it must be mixed with a plasticizer
and undergo a de-structuring procedure to be processed by injection, blow molding and extrusion
(Thuwall, 2006).
In Chapter 10, the authors deal with composites which are composite materials that are
characterized by exceeding the properties of the materials if they were used individually and by
possessing specific properties and characteristics. These materials are made up of two phases; a
continuous one called matrix and another dispersed called reinforcement. The reinforcement
provides the mechanical properties to the composite material and the matrix provides thermal
and environmental resistance. The matrix and the reinforcement are separated by the interface.
Composite materials are classified according to their structural components: fibrous, laminated and
particulate (Lubin, 2013).
In the gradual interest of finding biodegradable materials to replace EPS expanded polystyrene
foam, different studies have focused on developing starch foams, which have been industrially
obtained by extrusion, although these biodegradable foams have properties similar to polystyrene
materials. Some studies have been carried out to improve its mechanical properties by adding cellulose
(Motloung et al., 2019), chitosan, sugar cane fibers (Debiagi et al., 2011), Yucca flour, corn fiber
(Sumardiono et al., 2021), bioplastic from banana peel (Castillo et al., 2015) and other biodegradable
polymers. This topic on biodegradable foams is addressed in the Chapter 11. Many of the alternatives
seek to take advantage of agricultural residues to obtain a sustainable and biodegradable product in
order to reduce the consumption of non-renewable sources in the coming years.
The variation of different external factors, especially temperature, cause changes in the shape of
polymers during their processing. Thus, heat-shrinkable polymers result from different heat stimuli
and therefore changes in their shape in Chapter 12 describes the advantages and disadvantages of
this kind of polymers. Currently, some studies focus on replacing synthetic materials with flexible
films from biodegradable sources (Montilla et al., 2016; Montilla and Joaquí, 2016), because of
the multiple applications that heat-shrinkable biodegradable polymers have. These heat-shrinkable
polymers have application in many fields: packaging (Khankrua et al., 2019), medical devices, drug
administration, intravenous needles (Xiao et al., 2019), electronic devices, digital storage media
(Cui et al., 2017), etc.
Some of the fundamental characteristics of polymers to be used in medicine, is that they must
be biocompatible, that its mechanical properties are suitable for use, that they are excretable and
non-toxic for the recipient and that they can be sterilized (Labeaga, 2018). Based on these antecedents
in Chapter 14 the health applications of biodegradable polymers are discussed. The most common
application of biopolymers in surgeries is for development of absorbable sutures, some examples