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Vegetable Oil-Based Polymers: Properties, Processing and Applications
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Nota: 5 de 5 estrelas5/5 (1 avaliação)
Duração: 611 páginas
- Editora:
- Elsevier Science
- Lançado em:
- Jul 10, 2012
- ISBN:
- 9780857097149
- Formato:
- Livro
Descrição
The growing need to find a sustainable, environmentally-friendly replacement for petroleum-based materials is fuelling the development of bio-based polymers from renewable resources. Amongst the most promising of these are vegetable oil-based polymeric materials. Vegetable oil-based polymers provides a comprehensive review of the research in this important field.
After an introduction to classification and polymerization, Vegetable oil-based polymers goes on to review the factors involved in polymer biodegradation. The extraction, purification and application of vegetable oils are then explored, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies. The book then reviews polyamides, polyolefins and vegetable oil-based hyperbranched polymers. It concludes with an analysis of vegetable oil-based polymer composites and polymer nanocomposites.
Vegetable oil-based polymers is an indispensable guide for all those involved in the research and development of biopolymers as well as the wide range of industries looking for more sustainable polymer materials. Provides a comprehensive review of recent research in the area of vegetable oil-based polymeric materials Discusses vegetable oils and their derivatives, biodegradable polymers and the fundamentals of polymers Explores the extraction, purification and application of vegetable oils, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies
After an introduction to classification and polymerization, Vegetable oil-based polymers goes on to review the factors involved in polymer biodegradation. The extraction, purification and application of vegetable oils are then explored, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies. The book then reviews polyamides, polyolefins and vegetable oil-based hyperbranched polymers. It concludes with an analysis of vegetable oil-based polymer composites and polymer nanocomposites.
Vegetable oil-based polymers is an indispensable guide for all those involved in the research and development of biopolymers as well as the wide range of industries looking for more sustainable polymer materials. Provides a comprehensive review of recent research in the area of vegetable oil-based polymeric materials Discusses vegetable oils and their derivatives, biodegradable polymers and the fundamentals of polymers Explores the extraction, purification and application of vegetable oils, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies
Ações de livro
Comece a lerDados do livro
Vegetable Oil-Based Polymers: Properties, Processing and Applications
Notas:
Nota: 5 de 5 estrelas5/5 (1 avaliação)
Duração: 611 páginas
Descrição
The growing need to find a sustainable, environmentally-friendly replacement for petroleum-based materials is fuelling the development of bio-based polymers from renewable resources. Amongst the most promising of these are vegetable oil-based polymeric materials. Vegetable oil-based polymers provides a comprehensive review of the research in this important field.
After an introduction to classification and polymerization, Vegetable oil-based polymers goes on to review the factors involved in polymer biodegradation. The extraction, purification and application of vegetable oils are then explored, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies. The book then reviews polyamides, polyolefins and vegetable oil-based hyperbranched polymers. It concludes with an analysis of vegetable oil-based polymer composites and polymer nanocomposites.
Vegetable oil-based polymers is an indispensable guide for all those involved in the research and development of biopolymers as well as the wide range of industries looking for more sustainable polymer materials. Provides a comprehensive review of recent research in the area of vegetable oil-based polymeric materials Discusses vegetable oils and their derivatives, biodegradable polymers and the fundamentals of polymers Explores the extraction, purification and application of vegetable oils, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies
After an introduction to classification and polymerization, Vegetable oil-based polymers goes on to review the factors involved in polymer biodegradation. The extraction, purification and application of vegetable oils are then explored, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies. The book then reviews polyamides, polyolefins and vegetable oil-based hyperbranched polymers. It concludes with an analysis of vegetable oil-based polymer composites and polymer nanocomposites.
Vegetable oil-based polymers is an indispensable guide for all those involved in the research and development of biopolymers as well as the wide range of industries looking for more sustainable polymer materials. Provides a comprehensive review of recent research in the area of vegetable oil-based polymeric materials Discusses vegetable oils and their derivatives, biodegradable polymers and the fundamentals of polymers Explores the extraction, purification and application of vegetable oils, along with vegetable oil-based polyesters and poly(ester amide)s, polyurethanes and epoxies
- Editora:
- Elsevier Science
- Lançado em:
- Jul 10, 2012
- ISBN:
- 9780857097149
- Formato:
- Livro
Sobre o autor
Niranjan Karak is Professor of Polymer Science and Technology and Head of the Chemical Sciences Department at Tezpur University, India. He has published over 87 research papers, two books and two chapters in two edited books, and also regularly acts as a reviewer for many international polymer journals.
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1
Fundamentals of polymers
Abstract:
This chapter discusses the fundamentals of polymers. It deals with the concept and importance, definition, classification, raw materials, polymerisation processes and techniques, modification and structure– property relationships of polymers. It also describes the basic properties of different additives used and the processing of polymers. Building on our basic knowledge of polymers and their properties allows the details of different vegetable oil-based polymers to be discussed, making the importance of this chapter undeniable. Finally, a journey of discovery into vegetable oil-based polymers follows from considering the potential, different applications and challenges of existing polymers.
Key words
polymer
definition
classification
structure–property relationship
application
1.1 Introduction
Polymers are composed of large molecules with a high molecular weight, unlike fine chemicals or small molecular compounds. These macromolecules are formed by covalent links of large numbers of simple repeating units with identical constituents, where the addition or subtraction of a few such units does not change the properties. The term ‘polymer’ is a combination of two Greek words: ‘poly’ meaning ‘many’ and ‘meros’ meaning ‘parts’ or ‘units’. A polymer is thus the sum of many parts or units. ‘Polymerisation’ is the process of forming polymers from their respective reactive units.
The small molecules which form repeating units are known as monomers. Monomers typically react in the presence of a catalyst or initiator to form a polymer. The number of repeating units present in each polymer chain is known as the ‘degree of polymerisation’ (DP) and is used to determine the molecular weight of the polymer by the following formula:
molecular weight = molecular mass of repeating unit X ‘DP’
The high molecular weight of polymers is a result of the high DP, given the number of monomers in each chain.
In a polymerisation process, different polymer molecules may have different numbers of repeating units in their chains and hence the chain lengths are different, even under the same set of reaction conditions in the same batch. This is because the number of reactions involved in the formation of each polymer molecule is very high, so controlling the number of repeating units in different molecules is extremely difficult. The chain length of one molecule will differ from other molecules in the same polymer. Thus the number of repeating units varies from chain to chain, even within the same batch of polymers, so only the average number is taken and the molecular weight is expressed as the average molecular weight.
Biopolymers are found in animal and plant sources. Natural polymers include protein-based fibres such as wool and silk (mainly polyamide), carbohydrate fibres such as flax and cotton (mainly cellulose) as well as in tree saps which produce amber and latex (mainly hydrocarbon). The term ‘polymer’ was first coined by Berzelius in 1833. However, it was only in the 1920s that the concept of a polymer as a long sequence of repeating units linked by covalent bonds, was presented by H. Staudinger. (Nobel prize winner for chemistry, 1953).¹ At the same time, Carothers also rationally synthesised polymers from their respective monomers by means of different polymerisation processes. In addition to the above, knowledge about the structures (i.e. composition, arrangement and spatial disposition of the repeating units of the polymer chains) became a part of scientific knowledge, enabling their use in different applications.
Since then, a large number of useful polymers have been developed, offering a large variety of properties and applications. This is made possible by the unique properties and structural versatility of polymers compared to other categories of materials such as ceramics and metals. The significance and utility of polymers is illustrated by the following facts.²
• They are versatile with respect to their feed stock resources. The same monomer or starting material of a polymer can be obtained from petroleum, forestry or agricultural products.
• They exhibit versatility in structure and hence in their properties. For example, polyurethanes may be obtained as foam, thermoplastic, elastomeric, resin, adhesive or sealant material, depending on the composition of their constituents and the conditions of polymerisation.
• The amount of energy required for processing is small. This is because of the low melting and softening points of polymers and their ease of solubility in a variety of solvents.
• Polymers can be modified easily because of their organic nature and the presence of a large numbers of modifiable active sites in their structures.
• Polymers are light in weight because of their low density and large volume. This is due to their long, coiled and entangled chain structure.
• Polymers may be mass produced within a short timescale. They are also versatile in relation to polymerisation and processing techniques.
• Because the long chain and organic nature of polymers enables a large number of secondary interactions, they can be easily decorated.
• Polymers can be manufactured at a low overall cost.
1.2 Classification
Polymers are generally classified into categories based on their source, mode of formation, main chemical linkages, structure, thermal response, type of repeating unit, physical properties and bio-degradation characteristics, and so on.³
1.2.1 Source
There are three different classes based on polymer source.
1. Natural polymers: These are obtained from natural sources, that is flora and fauna. Examples are natural rubber (NR), wool, cellulose and silk. These are also known as biopolymers.
2. Semi-synthetic polymers: Chemically modified natural polymers are classified as semi-synthetic polymers. Some examples are epoxidised natural rubber (ENR), chlorinated natural rubber (Chlororub), nitrocellulose, carboxy methyl cellulose (CMC) and cellulose acetate.
3. Synthetic polymers: Synthetic polymers are obtained from their respective monomer(s) or reactants by chemical reactions in the laboratory. Most polymers fall into this category. Some examples are polyethylene, polypropylene, phenol-formaldehyde resin and styrene-butadiene rubber.
Polymers obtained from natural resources such as vegetable oils, animal fats and insects are known as bio-based polymers. They are natural derivatives of synthetic polymers rather than completely natural or completely synthetic polymers.
1.2.2 Mode of formation
Polymers can be classified into three categories: addition, condensation and rearrangement, based on their mode of formation.
Addition polymers
Addition or chain growth polymers are formed by the direct addition of monomer molecules held together by a covalent bond without loss of any by-product during the polymerisation process. Thus the molecular mass of a monomer molecule and a repeating unit is the same. Examples of this class of polymers are vinyl polymers such as polystyrene, polybutadiene and poly(vinyl chloride), and diene polymers such as polybutadiene, and poly-isoprene, polychloroprene.
Condensation polymers
Condensation or step growth polymers are formed by the incremental growth of monomer(s) or condensed product(s) of the reactant molecules through covalent bonds after the elimination of by-products such as H2O, NH3, HCl, HCHO, phenol, and so on. The molecular mass of a repeating unit is less than the molecular mass of a monomer(s) or reactant(s). Examples of this class of polymer are nylons, polyesters, polyimides and polycarbonates.
Rearrangement polymers
These polymers are formed by rearrangement of the monomer(s) or reactant(s) in an incremental manner, without elimination of any byproducts. Though they do not fall into either of the previous two classes, they exhibit some characteristics of both; for example, polyurethane, which is formed by a step growth polymerisation mechanism. It is not formed by condensation (as no by-product is formed), nor is it an addition polymer, as it is not formed by chain growth mechanism.
Although the terms addition or chain growth, and condensation or step growth are often used synonymously, they are not exactly the same. The classification of addition and condensation is based on the composition of the repeating unit and monomers or reactants used, whereas the classification of chain growth and step growth is based on the mechanism of the formation of the polymers.³
1.2.3 Main chemical linkages
Polymers are classified according to the main chemical linkages present in their structures. Based on this criterion, they may be classified as tabulated in Table 1.1. This classification is widely used in industry and is also of use in studying a particular class of polymers.²
Table 1.1
Classes of polymers with their corresponding main linkages and examples
1.2.4 Structure
The structure of a polymer includes both its physical and chemical structures. Polymers can be classified according to their structures in several ways.
Line structural representation of polymers can be demonstrated as line, as branched or cross-linked or three-dimensional:
• Linear polymers – The structure of these polymers may be represented by a simple line of defined length. Linear polyethylene, polybutadiene and nylon-6, are examples of this class of polymers.
• Branched polymers – The structure of branched polymers may be represented by a line of defined average length with short or long side lines. The branches may form during an uncontrolled polymerisation reaction or may result from the deliberate grafting of another monomer onto a polymer. Examples are branched polyethylene, graft copolymer of polystyrene on polybutadiene and vegetable oil-based highly branched polyester resins.
• Crosslinked or three-dimensional network polymers – Crosslinked polymers may be represented as a three-dimensional network structure. They are crosslinked, that is they consist of insoluble and infusible threedimensional giant molecules. Examples are thermosetting polymers such as crosslinked rubbers, resins, and so on.
Polymers may be classified into three categories according to their tacticity (symmetry), that is the arrangement of asymmetric carbon atoms in the main chain of the polymer:
• Isotactic polymers – The arrangement of all the asymmetric carbon atoms of the polymer chain is constant, that is the configuration of each repeating unit is identical (all ‘d’ or all ‘l’) for such polymers. An example is isotactic polypropylene.
• Syndiotactic polymers – The arrangement of any two consecutive asymmetric carbon atoms of the polymer chain varies regularly (alternative ‘d’ and ‘l’). An example is syndiotactic polypropylene.
• Atatic polymers – The arrangement of the asymmetric carbon atoms in the polymer chains are completely random (random ‘d’ and ‘l’) and no proper sequence is maintained. An example is atactic polypropylene.
Polymers may also be classified as follows, according to the degree of crystallinity in their structures:
• Crystalline polymers – Crystalline polymers have a certain degree of crystallinity in their structures owing to the long range order arrangement of some segments of the polymer chains. High density polyethylene, isotactic polypropylene and Kevler are examples of these polymers.
• Amorphous or non-crystalline polymers – These polymers do not have any degree of crystallinity. Examples of these polymers are butadiene rubber and atactic polypropylene.
It should be noted that some polymers may generate crystallinity at a certain concentration of their solution (lyotropic) or under melting conditions (thermotropic). These are known as liquid crystalline polymers and behave like an isotopic liquid. They exhibit high strength properties.
Polymers may be further classified as cis-isomer and trans-isomer, based on the geometrical isomerism of the repeating units. Examples are cis-1, 4-polyisoprene (natural rubber) and trans-1,4-polyisoprene (Gutta percha, plastic). There are also three different classifications of polymers based on the chemical constituents present in the structures.
• Organic polymer – The main element in the chain of these polymers is carbon, along with the other elements such as ‘H’, ‘O’ and ‘N’. Most polymers are included in this class. Examples are polyethylene, poly(vinyl chloride), styrene-butadiene rubber and nylons.
• Inorganic polymers – The main elements in the chain of these polymers can be any one, or more than one, of inorganic elements such as ‘Si’, ‘P’, ‘S’ and ‘N’. These may or may not have any carbon atoms in their main chain. However, in the side chain, carbon containing moieties are generally present. Examples of this class are silicone polymers and phosphorous polymers.
• Organometallic polymers – The chains of these polymers contain both carbon and metallic elements. They are also known as metal-containing polymers. Examples are: antimony-containing polymers, arsenic-containing polymers, and so on.⁴
1.2.5 Thermal response
Polymers may be classified as follows, according to their thermal response.
Thermoplastic polymers
These polymers can be repeatedly softened by heating under certain conditions. The temperature at a specified pressure should be much lower than the decomposition temperature of the polymer. They can be transformed on cooling into hard materials without any change in their properties. Some examples of this class of polymers are polyethylene, polypropylene and polystyrene.
Thermosetting polymers
These polymers are soluble in a variety of solvents before setting. They are fusible and flowable under certain conditions before the formation of three-dimensional structures in the finished state. But they are transformed permanently to an insoluble, infusible and dimensionally stable mass once they are chemically cross-linked. Examples of this class of polymers are vulcanised rubbers, cross-linked polyethylene, cross-linkable resins, and so on.
1.2.6 Type of repeating unit
Polymers are placed in two different classes according to the type of repeating units present in the molecular chain.
Homopolymers
These polymers have only one type of repeating unit. Polyethylene, poly(vinyl chloride), poly(ethylene terephthalate), etc. are a few examples of this class of polymers.
Copolymers
These polymers have more than one type of repeating unit in their structure. They are also known as heteropolymers. Examples are poly(ethylene-co-propylene), poly(styrene-co-butadiene) and poly(acrylonitrile-co-butadiene-co-styrene).
Based on the arrangements of the repeating units in the structure of the copolymers, these polymers can be sub-classified as follows:
• Random copolymer – Copolymers with two or more numbers of repeating units (A and B) are arranged randomly in the chain. They may be represented schematically as –A-B-A-A-A-B-B-A-B-B-B-A-. Poly(ethylene-ran-polypropylene) (EPR rubber) is an example of this type of polymer.
• Alternating copolymers – Copolymers with two or more repeating units (A and B) are alternately arranged in the chain. They may be represented schematically as –A-B-A-B-A-B-A-B-A-B-A-B-. Poly(styrene-alt-butadiene) and alternate poly(butadiene-co-acrylontrile) are examples of this class of polymers.
• Block copolymers – Copolymers with two or more repeating units (A and B) are arranged in a block within the chain. They may be represented schematically as –A-A-A-A-A-B-B-B-B-B-B-B-A-A-A-A-B-B-B-. Poly(butadiene-block-styrene) is an example of a block copolymer.
• Graft copolymers – These consist of two or more homopolymers, where one homopolymer is covalently attached or grafted as a long branch to the spine of another homopolymer. Examples are poly(acrylonitrile-graft-vinyl acetate) and poly(acrylonitrile-graft-methacrylic acid).
1.2.7 Physical properties
Polymers can be grouped into four classes according to their physical properties.
Rubbers or elastomers
These polymers readily undergo high, reversible elongation (extension) under relatively low applied stress. They are high molecular weight (10⁵ to 10⁶ g mol−1) amorphous polymers with a low glass transition temperature (generally much lower than room temperature) and high chain flexibility, with low secondary forces between the chain molecules. Dimensional stability in these polymers can be obtained through the chemical cross-linking, known as vulcanisation, or through blending with plastic (thermoplastic elastomer) for their end applications. Natural rubber, polybutadiene, poly-chloroprene and styrene-butadiene copolymer (SBR) are examples of this class of polymers.
Plastics
The intra-inter-molecular attraction forces and the strength properties are higher in plastics than in rubbers but the elongation at breaking is lower. They possess a certain degree of crystallinity and the glass transition temperature is generally higher than room temperature. Plastics usually soften without decomposition on heating and are transformed into dimensionally stable, hard materials after repeated cooling undertaken with some precautions. Polyethylene, polypropylene, polystyrene and poly(methyl methacrylate) are examples of this type of polymer.
Fibres
These polymers have the highest strength and crystallinity but the lowest elongation among the different classes of polymers. They have very high intra-/inter-molecular attraction forces between the chain molecules by means of polar–polar, polar–induced polar, H-bonding, and so on, along with van der Waals forces. The glass transition temperatures for these polymers are much higher than room temperature. However, they must be drawn into filaments (fibres) by solution and/or by melt spinning techniques. Some examples of fibres are nylons, Kevler and poly(ethylene terephthalate).
Resins
When the number of repeating units in a polymer chain is low, that is when the molecular weight of the polymer is low (2000–10000 g mol−1), the polymer is defined as a resin, provided it possesses sufficient numbers of active sites in its structures for chemical cross-linking to occur. The resins can form three-dimensional network structures if sufficient external energy (heat/light/radiation) is applied, with or without the use of any other chemical(s) in their finished state. They are free flowing materials of low viscosity. Polyester resins, epoxy resins, and polyurethane resins are examples of this type of polymer. This book contains descriptions of the different types of resins derived from various vegetable oils.
1.2.8 Biodegradable characteristics
Based on this criterion, polymers may be classified into two categories.
Biodegradable polymers
These polymers, which are degradable by a variety of micro-organisms under normal environmental conditions, are known as biodegradable polymers.⁵ They are mainly biopolymers obtained directly from natural materials, or bio-based polymers which are obtained from renewable resources. These are the most effective polymers with regard to solid waste management problems. The oil is obtained from natural resources and the polymers have biodegradable linkages. Examples of this type are polylactide, collagen and natural rubber. Biodegradable polymers are described in the next chapter.
Non-biodegradable polymers
Polymers that do not degrade under normal environmental conditions, are termed non-biodegradable. Most synthetic polymers are included in this category and their wide use presents a danger to the environment.
1.3 Raw materials for polymers
The main constituents of polymers are carbon, hydrogen, oxygen and nitrogen, although a few polymers may also contain other elements such as silicone, phosphorous, sulphur, metals and metalloids. The basic raw materials for polymers are petroleum, coal, natural gas, forestry products, agricultural products, biomass, and so on.² From these raw materials, a variety of different monomers are obtained: initiators (to initiate polymerisation), catalysts (to catalyse polymerisation), retardants (to slow down polymerisation or cross-linking reactions), inhibitors (to inhibit the polymerisation reaction), chain regulators (to regulate the chain length of a polymer), additives (incorporated in polymers to improve their performance), solvents, and so on. The main source of these chemicals is petroleum. They can be obtained directly from petroleum by cracking followed by fractionation, or by a chemical transformation of the fractionated products. For example, olefin monomers like ethylene and propylene are obtained directly from naphtha cracking as C2 and C3 fractions, whereas styrene and butadiene, are obtained after suitable chemical transformations of C6 and C4 fractions, respectively. (The digit indicates the number of carbon present in the components.) Similarly, some main and auxiliary chemicals for polymers can be produced from coal and natural gas. Although, agricultural and forestry products and biomass were formerly used, they were largely abandoned after the development of economically acceptable commercial systems for obtaining a variety of chemicals from crude oil, natural gas and coal. However, these sources are again becoming critical because of declining crude oil reserves, global warming, and societal, economical and environmental concerns. Among the different natural renewable resources, vegetable oils are the most important and the polymers derived from them are the subject of this
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