Synthesis and Characterization of Sustainable and Biobased Copolymers from Lignocellulosic

Synthesis and Characterization of Sustainable and Biobased Copolymers from Lignocellulosic
Author: Guery Saenz
Publisher:
Total Pages: 0
Release: 2022
Genre:
ISBN:

Natural compounds have been the primary resource used to produce polymeric materials by humankind since the mid-1900s. Yet, progress in bio-based polymers from renewable feedstock has encountered some obstacles, mainly due to the low prices of petroleum-based monomers, compared to natural and sustainable materials. However, most commodity plastics are non-degradable materials, and solid plastic waste accumulation adversely affects the environment. As the world population is growing and demanding chemicals, energy, and plastics materials, polymer research is focusing on synthesizing bio-based and degradable polymers. Thus, biomass, a sustainable and inexpensive feedstock, is highly appropriate for designing alternative thermoplastics that are degradable to reduce the current environmental issues. In this dissertation, three different approaches were used to afford alternative thermoplastics to petroleum‐based commodities: bio-based poly(ether-amide)s, random aromatic copolyesters, and copoly(acetal triazole)s. In our first approach, two new lignin‐derived poly(ether‐amide)s (PEA)s were prepared. Their thermal properties showed high degradation temperature (Td) ranging from 330 °C to 380 °C, and glass transition temperature (Tg) between 100 °C and 120 °C. The chemical degradation studies revealed that the PEAs were degradable in 4 M H2SO4, HNO3, and TFA in 3 days. The second polymer group synthesized were semicrystalline bio-based aromatic copolyesters with tunable thermal properties. The thermal analysis of these copolyesters revealed high Td (413 °C to 446 °C) and Tg and Tm ranging from –36 °C to 67 °C and 60 °C to 267 °C, respectively. Their crystallization behavior showed a dependence on the comonomer composition, exhibiting a pseudo-eutectic region. Finally, furfural- and benzaldehyde-based copoly(acetal triazole)s (Td range 280–340 °C) were prepared by click polymerization at room temperature. Preliminary results showed that furfural-based copoly(acetal triazole)s were susceptible to hydrolytic degradation under neutral conditions after only 8 days at 40 °C. Overall, degradable and bio-based polymers were successfully synthesized as a potential thermoplastic alternative for packaging applications.

Synthesis and Characterization of Copolymers from Lignin

Synthesis and Characterization of Copolymers from Lignin
Author: Hui Li
Publisher:
Total Pages: 346
Release: 2014
Genre: Copolymers
ISBN:

Development of bio-based materials, especially from agricultural and forestry industrial byproduct streams, is urgent and necessary under the circumstances of sustainability and the environment. Industrial lignin is an underutilized biopolymer byproduct from both the pulping and cellulosic ethanol biorefinery industries with tremendous availability, showing potential as a substrate for producing biobased polyester materials because of its structure and abundance of hydroxyl functional groups. In this study, lignin based copolymeric elastomers were synthesized by simple one pot two step polycondensation of methanol soluble (MS) fractions of industrial lignins and a series hyperbranched prepolymers (HBP) with different branching and core structures using various multifunctional monomers. Specifically, three industrial lignins (Indulin AT Kraft softwood (IN), Protobind 1000 (PB), and corn stover (CS)) were first subjected to methanol fractionation and then to a detailed chemical and thermal characterization. Fractionation and characterization of three industrial lignins were carried out to provide a hard (or netpoint) segment substrate for the copolymer synthesis. Correlations between chemical and thermal properties were observed in terms of condensation index, hydroxyl group, and molar mass versus the glass transition temperature (Tg̳). A series of lignin-copolymers were prepared using the three different lignins and a HBP composed of triethanolamine (TEA, trifunctional) and adipic acid (AA, difunctional), A2B3) to evaluate the effects of lignin types and lignin contents. Tensile properties were dominated by HBP 45% lignin content while lignin dominated at 45% content. The copolymers Tg̳ increased with lignin content, while lignin type did not play a significant role. Thermally-stimulated dual shape memory effects (Ts̳-SME) of the copolymers were obtained and quantified by cyclic thermomechanical tests. All copolymers had shape fixity rate 95% and shape recovery >90% for all copolymers. The copolymer shape memory transition temperature (Tt̳r̳a̳n̳s̳) increased with lignin content and Tt̳r̳a̳n̳s̳ was 20°C higher than Tg̳. To obtain different HBP structure, a prepolymer was synthesized composing of long alkyl (C12) chain diacid (DDDA), TEA, and tris(hydroxymethyl)aminomethane (THAM, tetrafunctional), B3-A2-CB31). The C12 diacid contributed to a partially crystalline structure, while THAM contributed to more branching as well as forming stiff amide linkages in the prepolymer. Lignin-copolymers were synthesized with these prepolymers and PB lignin. Tensile properties were dominated by HBP 25% lignin content while lignin dominated 25% content. The Tg̳s of copolymers increased with lignin content. The lignin-copolymer with 30% lignin content demonstrated optimal mechanical properties (tensile strength 5.3 MPa, Young's modulus 8.9 MPa, strain at break 301%, and toughness 1.03 GPa). Good Ts̳-SME was obtained and could be tailored by lignin content and activation temperatures ranged between ambient and body temperature. Finally, in order to pursue higher biobased content in the lignin-copolymers, HBP were prepared from AA, Glycerol (Gly, trifunctional), and enhanced by additions of diisopropanolamine (DIPA, trifunctional), or THAM, B2B32-A2, B2B32-DB42- A2, and B2B32-CB13- A2) to form branched to hyper branched structures. The higher branching crosslinkers, DIPA and THAM, were shown to influence the chemical and thermal properties of the prepolymers. The highly biobased lignin-copolymers demonstrated good shape memory and elastic properties. Tt̳r̳a̳n̳s̳ could be tuned by variations of Gly, DIPA and THAM proportions for applications under different temperature circumstances. Different branching and core structures of prepolymers (soft segment) were shown to influence the properties prepolymers and corresponding lignin-copolymers. All the lignin-copolymers were shown to be elastomeric and possess great Ts̳-SME. The results demonstrated that properties of lignin-copolymers could be tuned through lignin type, lignin content, prepolymer structure, and monomer variations. This study demonstrated that lignin, a renewable byproduct, can be promisingly valorized to apply as a netpoint segment in biobased polymer systems with SME behavior. [Letters with double underscore are subscript.]

Green Polymer Chemistry

Green Polymer Chemistry
Author: H. N. Cheng
Publisher: ACS Symposium
Total Pages: 0
Release: 2015
Genre: Science
ISBN: 9780841230651

Green chemistry is the design of chemical products and processes that reduce or eliminate the use or generation of hazardous substances. Green polymer chemistry is an extension of green chemistry to polymer science and engineering. Developments in this area have been stimulated by health and environmental concerns, interest in sustainability, desire to decrease the dependence on petroleum, and opportunities to design and produce "green" products and processes. Major advances include new uses of biobased feedstock, green reactions, green processing methodologies, and green polymeric products. A current feature of green polymer chemistry is that it is both global and multidisciplinary. Thus, publications in this field are spread out over different journals in different countries. Moreover, a successful research effort may involve collaborations of people in various disciplines, such as organic chemistry, polymer chemistry, material science, chemical engineering, biochemistry, molecular biology, microbiology, enzymology, toxicology, environmental science, and analytical chemistry. This book combines the major interdisciplinary research in this field and is targeted for scientists, engineers, and students, who are involved or interested in green polymer chemistry. These may include chemists, biochemists, material scientists, chemical engineers, microbiologists, molecular biologists, enzymologists, toxicologists, environmental scientists, and analytical chemists. It can be a textbook for a course on green chemistry and also a reference book for people who need information on specific topics involving biocatalysis and biobased materials.

Sustainability of Biomass through Bio-based Chemistry

Sustainability of Biomass through Bio-based Chemistry
Author: Valentin I Popa
Publisher: CRC Press
Total Pages: 353
Release: 2021-03-22
Genre: Technology & Engineering
ISBN: 1000358283

The process of photosynthesis is a potential source of energy and bioproducts. Renewable sources of polymeric materials offer an answer to maintaining sustainable development of economically and ecologically attractive technology. The innovations in the development of materials from biopolymers, preservation of fossil-based raw materials, complete biological degradability, reduction in the volume of garbage and compostability in the natural cycle, climate protection through reduction of carbon dioxide released, and the application possibilities of agricultural resources for the production of bio/green materials are some of the reasons why such materials are attracting public interest. FEATURES Discusses waste from urban areas, forestry and agricultural processes, specifically grown crops such as trees, starch crops, sugar crops hydrocarbon plants and oils, and finally aquatic plants such as water seaweeds and algae, which can be used as raw materials for sustainable development. Presents recent advances in the development of some specifically chemical components of biomasses for a sustainable future. Focuses on lignocellulose as a source of bio-based products. Draws upon expertise from various countries. Describes how upgraded and integrated biomass processing may reduce the risks associated with the COVID-19 pandemic. Valentin I. Popa is professor emeritus of Wood Chemistry and Biotechnology at Gheorghe Asachi Technical University of Iasi, Romania.

Biopolymers and Composites

Biopolymers and Composites
Author: Samy A. Madbouly
Publisher: Walter de Gruyter GmbH & Co KG
Total Pages: 394
Release: 2021-10-04
Genre: Technology & Engineering
ISBN: 1501521942

The growing interest in replacing petroleum-based products by inexpensive, renewable, natural materials will have a significant impact on sustainability, environment, and the polymer industry. This book provides scientists a useful framework to help take advantage of the latest research conducted in this rapidly advancing field enabling them to develop and commercialize their own products quickly and more successfully.

Lignin Chemistry

Lignin Chemistry
Author: Yuhe Liao
Publisher: John Wiley & Sons
Total Pages: 498
Release: 2024-05-31
Genre: Science
ISBN: 3527839852

Lignin Chemistry A thorough reference guide to Lignin Chemistry, from inherent structure revealing to transformation into chemicals, fuels, and materials Climate change, driven by rising greenhouse gas emissions, is the defining challenge of our time. Reducing our dependence on non-renewable resources such as fossil fuels will require alternative, more sustainable resources. Lignin, the only widely-occurring, renewable, aromatic bio-polymer in Nature, has a range of application potential in the production of chemicals, fuels, and other industrial materials. Lignin science has become one of the fastest-growing and most significant areas of sustainable chemistry in the world. Lignin Chemistry: Characterization, Isolation, and Valorization presents a systematic, multidisciplinary overview of this cutting-edge field and its current state of research. Beginning with a robust characterization of lignin, the book addresses the isolation and transformation of lignin, as well as the book inspires with a plethora of applications. The result is a critical resource for researchers and professionals in any area of academic or industry where renewable biomass, in particular lignin, has importance. Lignin Chemistry readers will find: Thermochemical and catalytic strategies for lignin conversion Detailed discussion of the valorization of lignin towards biopolymers, nanoparticles, carbon fibers and materials, and hydrogels An authorial team with immense and varied research experience Lignin Chemistry is ideal for chemical engineers, catalytic chemists, biochemists, material scientists, and analytical chemists in industry.

Lignocellulosic Materials and Their Use in Bio-based Packaging

Lignocellulosic Materials and Their Use in Bio-based Packaging
Author: Lina Fernanda Ballesteros
Publisher: Springer
Total Pages: 107
Release: 2018-06-18
Genre: Science
ISBN: 3319929402

This brief provides a comprehensive review of lignocellulosic materials and their primary role in the future development of bio-based packaging. Topics such as: sources and extraction methods of lignocellulosic materials; main constituents of lignocellulosic materials; functionality of lignocellulosic materials; the development of bio-based and biodegradable packaging; incorporation of lignocellulosic materials in bio-based packaging materials; properties and functionality of bio-based packaging, are discussed by authors who are experts in the field.

Green Approach to Alternative Fuel for a Sustainable Future

Green Approach to Alternative Fuel for a Sustainable Future
Author: Maulin P Shah
Publisher: Elsevier
Total Pages: 526
Release: 2023-05-14
Genre: Technology & Engineering
ISBN: 0128243198

Green Approach on Alternative Fuel for Sustainable Future addresses the advancement of biological and biochemical technologies in context to alternative fuel synthesis. This book emphasizes and discusses the technology involved and development on the status of alternative fuel production and related aspects, including biofuel production. The potential uses of waste material to turn them into wealth, as alternative energy sources also been discussed. The extended and detailed content of the book also covers the promising uses of microalgae treatment to produce biofuel. By not being limited to the biological aspect the book also discusses and explores the perspective of green chemistry for energy production. By adding policy and commercialization, the book provides comprehensive information, from lab to field, with extensive illustrations, case studies, summary tables and up-to-date references. Gives an overall overview on general and applied aspects on biofuels Provides scientific methodology for viable sustainable transition strategies for policy makers Outlines green technologies to face the environmental crisis and allow for the transformation into a sustainable future Provides data-based information in context to advance and innovative technology Explore possibilities and limitation of expansion and commercialization of biofuels Offers accumulation of innovative approach to promoting sustainable development Includes cutting-edge research concepts for biofuels production

Bio-Based Epoxy Polymers, Blends, and Composites

Bio-Based Epoxy Polymers, Blends, and Composites
Author: Jyotishkumar Parameswaranpillai
Publisher: John Wiley & Sons
Total Pages: 402
Release: 2021-04-26
Genre: Technology & Engineering
ISBN: 3527346481

State-of-the-art overview on bioepoxy polymers as well as their blends and composites -- covering all aspects from fundamentals to applications! Bioepoxy polymers is an emerging area and have attracted more and more attention due to their biodegradability and good thermo-mechanical performance. In recent years, research progress has been made in synthesis, processing, characterization, and applications of bioepoxy blends and composites. Bioepoxy polymers are very promising candidates to replace the traditional thermosetting nonbiodegradable polymers. Bio-Based Epoxy Polymers, Blends and Composites summaries recent research progress on bioepoxy polymers as well as their blends and composites. It covers aspects from synthesis, processing, various characterization techniques to broad spectrum of applications. It provides a correlation of physical properties with macro, micro and nanostructures of the materials. Moreover, research trends, future directions, and opportunities are also discussed. Attracts attention: Bioepoxy polymers are environmentally friendly and considered as a promising candidate to replace the traditional thermosetting nonbiodegradable polymers Highly application-oriented: Bioepoxy polymers can be used in a broad range of applications such as polymer foams, construction, aerospace, automobiles, self-healing systems One-stop reference: Covers all aspects of bioepoxy polymer, their blends and composites, such as synthesis, properties, processing, characterization and applications Broad audience: Attracts attention from both academia and industry