Madbouly / Zhang / Kessler Bio-Based Plant Oil Polymers and Composites

1. Auflage 2015
ISBN: 978-0-323-37128-5
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 230 Seiten

Reihe: Plastics Design Library

Bio-based Plant Oil Polymers and Composites provides engineers and materials 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. Plant oil is one of the most attractive options as a substitute for non-renewable resources in polymers and composites, and is producing materials with very promising thermomechanical properties relative to traditional, petroleum-based polymers. In addition to critical processing and characterization information, the book assists engineers in deciding whether or not they should use a plant oil-based polymer over a petroleum-based polymer, discussing sustainability concerns, biodegradability, associated costs, and recommended applications. The book details the advancements in the development of polymeric materials and composites from plant oils, and provides a critical review of current applications in various fields, including packaging, biomedical, and automotive applications. Also includes the latest progress in developing multifunctional biobased polymers-by increasing thermal conductivity or adding antibacterial properties, for example. - Essential coverage of processing, characterization, and the latest research into polymeric materials and composites derived from plant oils (thermoplastics, thermosets, nanocomposites, and fiber reinforced composites) - Critically reviews the potential applications of plant oil-based polymers, including sensors, structural parts, medical devices, and automotive interiors - Includes the latest developments in multifunctional bio-based polymer composites

Samy Madbouly is a Materials Scientist at Pacific Northwest National Laboratory, Richland, WA, USA. He received his Ph.D. from the Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Japan. He served as a senior research scientist at the School of Polymers and High-Performance Materials, University of Southern Mississippi, USA, and at the Center for Biomaterial Development, Institute of Polymer Research, GKSS, Germany. He also worked as assistant Professor in the Department of Materials Science and Engineering at Iowa State University and School of Engineering at Pennsylvania State University, as well as a Senior Polymer Engineer at Schlumberger, USA.

Autoren/Hrsg.

Madbouly, Samy

Zhang, Chaoqun

Kessler, Michael R.

Leseproben

2

Plant Oil-Based Derivatives

Chaoqun Zhang1

Samy A. Madbouly2,3
1    Department of Mechanical Engineering, Texas A&M University, College Station, TX, USA
2    Department of Chemistry, Faculty of Science, Cairo University, Orman-Giza, Egypt
3    Department of Materials Science and Engineering, Iowa State University, Ames, IA, USA

Abstract

Plant oils are renewable and environmental friendly natural resource with excellent properties, including ready availability, inherent sustainability, and relatively low cost. Due to depleting fossil resources, the ever-increasing emission of greenhouse gases and toxic waste, there has been increased interest in developing plant oil-based alternatives to petroleum-based products. The inherent functionality (carbon double bonds, ester, and so on) offers the possibility of these renewable resources being transformed into industrially significant compounds via several efficient processes. Some of these compounds are considered bio-build block for making polymeric materials, which would be focus on the following chapter. This chapter discusses the plant oil-based derivatives directly used as the valuable compounds for industry application.

Keywords

plant oils

fatty acids

alcohols

fatty amides

fatty amines

ester derivatives

Outline

2.1 Introduction 19

2.2 Plant Oil-Based Derivatives 21

2.2.1 Fatty Acids 21

2.2.2 Fatty Amides/Nitriles/Amines 21

2.2.3 Alcohols 22

2.2.4 Ester Derivatives 25

2.2.5 Epoxy Derivatives 28

2.2.6 Conjugates 30

2.2.7 Other Derivatives 31

2.3 Conclusions 32

References 33

2.1. Introduction

The depleting of fossil resources, the ever-increasing emission of greenhouse gases and toxic waste, and stringent environmental regulation have triggered an increasing interest in developing industrially compounds and polymers from natural resources as an alternative of petroleum-based counterparts [1,2]. Various renewable resources are available, including cellulose, starch, natural oils, and sugars. Among them, plant oils are among the most promising options; they offer excellent properties, including world-wide availability, inherent sustainability nature, and relatively low price [3,4]. A large number of plant oils, such as soybean oil, rapseed oil, and palm oil, are considered to be the most important renewable feedstock processed in the chemical industry to decrease the dependence on depleting petroleum resources.

Vegetable oils are esters formed between glycerin and different fatty acids containing from 8 to 24 carbons and from 0 to 7 carbon–carbon double bonds (see Table 2.1), depending on the plant type and climatic conditions of harvest. Typical structure of vegetable oils is shown in Figure 2.1. Naturally existing carbon double bonds in most vegetable oils are located in the 9–16th carbon, which makes them less reactivity due to radical trapping by allyl hydrogens from methylene group between double bonds. However, in some oils, such as Tung oil, conjugated double bonds are available, which demonstrate high polymerization activity. Ester group is another reactive site for most of vegetable oils, and some oils contain other reactive groups such as hydroxyl or epoxy as shown in Table 2.2. For example, castor oil contains 90% ricinoleic acid, which contains ne hydroxyl group on 12th carbon. Vernonia oil has a functionality of 2.8 epoxy rings per triglyceride. All these inherent functionalities offer the possibility of these renewable resources being transformed into industrially significant compounds (fatty acid, fatty amides/nitriles/amines, alcohols, ester derivatives, epoxy, conjugates) via several efficient chemical modifications. The basic oleochemicals are fatty acids (ca. 52%), the respective methyl esters (ca. 11%), amines (ca. 9%), and alcohols (ca. 25%) [1].

Table 2.1

Degree of Unsaturation, Composition of Common Vegetable Oils

Double Bonds

Fatty Acid Composition (%)

Palmitc

Stearic

Oleic

Linoleic

Linolenic

Castor

3.0

1.5

0.5

5.0

4.0

0.5

Corn

4.5

10.9

2.0

25.4

59.6

1.2

Linseed

6.6

5.5

3.5

19.1

15.3

56.6

Olive

2.8

13.7

2.5

71.1

10.0

0.6

Palm

1.7

42.8

4.2

40.5

10.1

-

Soybean

4.6

11.0

4.0

23.4

53.3

7.8

Canola

3.9

4.1

1.8

60.9

21.0

8.8

Figure 2.1Typical structure of vegetable oils (R1, R2, R3 represent fatty acid chains).

Table 2.2

Six Common Fatty Acids Composition in Vegetable Oils

Fatty Acids

Formula

Structure

Caprylic

C8H16O2

Palmitc

C16H32O2

Stearic

C18H36O2

Oleic

C18H34O2

Linoleic

C18H32O2

Linolenic

C18H30O2

Ricinoleic

C18H34O3

a-Eleostearic

C18H30O2

Vernolic

C18H32O2

The world production of major vegetable oils has risen from 95 million tons in 2002/2003 to 154 million tons in 2012/2013 at an average rate just over 5 million tons a year [1]. Soybean oil, palm oil, and rapeseed oil range highest world production of vegetable oils. Most of the global soybean oil production is located in North America and South America. For example, in the United States, the three largest crops planted are corn, soybean, and wheat with planted acreage of 30%, 28%, and 23%, respectively. However, rapeseed production is the major crop in Europe, while palm oil dominates in Asia. These three oils are the most attractive for large-scale industrial products due to low price. From 2001 to 2005, 15% of soybean oil was used for industry application [5]. Although the majority of vegetable oils are primarily produced for food and feed purposes, minor vegetable oils such as castor and linseed oil are almost solely used for industrial applications.

Recently, there has been a steady growth in the use of plant oils in the painting and coating industries, such as shampoos lubricants, emulsifiers, cosmetics, plasticizers, biodiesels and pharmaceuticals, as well as various polymeric materials.

2.2. Plant Oil-Based Derivatives

2.2.1. Fatty Acids

The hydrolysis or saponification of different vegetable oils under the influence of water, temperature, pressure, and catalyst produces a mixture of C6 up to C20 fatty acids. Partial hydrolysis of triglycerides yields mono- and di-glycerides and fatty acids, while complete hydrolysis generates glycerol and fatty acids as shown in Figure 2.2. Generally, the reaction between plant oils and water is pretty slow due to the hydrophobic nature of plant oils. Increased temperature or pressures improve the solubility of plant oils in water, leading to rapid hydrolysis rates [6]. Also, organic acid (such as HCl, H2SO4) and basic (NaOH) can be used to accelerate the reaction. When basic is used, the final product is fatty acid sodium salts, which are used to make soaps, skin products, candles, and perfumes.

Figure 2.2Hydrolysis of vegetable oils.

Also, fatty acids provide useful chemicals for polymers development. For example, castor oil fatty acids were used as ring opener for preparation of polyols for polyurethane coating and foam [4].

2.2.2. Fatty Amides/Nitriles/Amines

Fatty amines can be obtained by hydrogenation of fatty nitriles, which are produced by the reaction between triglycerides, or fatty acids, or fatty esters and ammonia with elimination of two molecules of water at high temperature (423–723 K) in the presence of dehydrating catalyst (such as silica gel, alumina, or iron-based catalysts, and so on) [6,7]. Actually, the products from the hydrogenation of nitriles are mixtures of primary, secondary, and tertiary amines as shown in...