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Polyurethane Polymers: Blends and Interpenetrating Polymer Networks
Ações de livro
Comece a lerDuração: 766 páginas46 horas
- Editora:
- Elsevier Science
- Lançado em:
- Aug 15, 2017
- ISBN:
- 9780128040850
- Formato:
- Livro
Descrição
Polyurethane Polymers: Blends and Interpenetrating Networks deals with almost all aspects of blends and IPNs formed by polyurethane, including the thermal, mechanical, morphological, and viscoelastic properties of each blend presented in the book. In addition, major applications related to these blends and IPNs are mentioned.
Provides an elaborate coverage of the chemistry of polyurethane, including its synthesis and properties Includes available characterization techniques Relates types of polyurethanes to their potential properties Discusses blends optionsAções de livro
Comece a lerDados do livro
Polyurethane Polymers: Blends and Interpenetrating Polymer Networks
Duração: 766 páginas46 horas
Descrição
Polyurethane Polymers: Blends and Interpenetrating Networks deals with almost all aspects of blends and IPNs formed by polyurethane, including the thermal, mechanical, morphological, and viscoelastic properties of each blend presented in the book. In addition, major applications related to these blends and IPNs are mentioned.
Provides an elaborate coverage of the chemistry of polyurethane, including its synthesis and properties Includes available characterization techniques Relates types of polyurethanes to their potential properties Discusses blends options- Editora:
- Elsevier Science
- Lançado em:
- Aug 15, 2017
- ISBN:
- 9780128040850
- Formato:
- Livro
Relacionado a Polyurethane Polymers
Amostra do livro
Polyurethane Polymers
Chapter 1
Polyurethanes
Structure, Properties, Synthesis, Characterization, and Applications
Arunima Reghunadhan and Sabu Thomas, Mahatma Gandhi University, Kottayam, Kerala, India
Abstract
The chapter gives an introduction to the polyurethane (PU) polymer, its synthesis and its structure. The chapter details the different methods of polyurethane synthesis, various starting materials and the necessary components required for PU synthesis. The chapter also deals with the phase separation process of polyurethane and the effect of phase separation on the morphology, thermal, and mechanical properties of PU. The application of spectral techniques such as FTIR and NMR in the structural determination of polyurethane are also covered.
Keywords
Polyurethane; structure; morphology; phase separation; spectra
Contents
1.1 Introduction 1
1.2 Types of Polyurethanes, their Properties and Applications 2
1.3 Synthesis and Chemistry of Polyurethanes 3
1.4 Structural Analysis of Polyurethanes 7
1.5 Phase Separation and Miscibility 8
1.6 Characterization of Polyurethanes 11
1.7 Conclusions 15
References 15
1.1 Introduction
Polyurethanes (PUs) are a versatile class of polymers in both synthesis and applications. The superior properties make them suitable for a wide range of applications. They have very good mechanical properties, chemical resistance, and resilience. The presence of reactive functionalities in the main chain of polyurethane increases its compatibility with most polymers and so is suitable for the formation of networked structures. Polyurethane differs from normal polymers in that there are no urethane monomers. The chemical linkage existing in the polymer is denoted as urethane (–NHCOO–) and is the most reactive moiety in the polyurethane. Dependent on the starting materials, the end product differs in its nature, properties, and applications. From its first synthesis in 1937 by the genius German chemist Prof. Otto Bayer through a normal polyaddition reaction, it has been the most demanded plastic all over the world. Otto Bayer is recognized as the father of polyurethane. The polyurethane synthesis chemistry is easy in its basics, but becomes complex in the laboratory setting. The variety in the starting material and the additives and catalysts makes the synthetic route complex.
Polyurethanes are synthesized by the addition of alcohols and isocyanates. Diols or polyols are the alcoholic part and the diisocyanates are reacted with them. As a good variety of both these components are available easily, a large variety of polyurethanes can be obtained. PU can be soft, as in the case of foams, or hard, as in the case of automotive parts. Polyurethane exists in may forms in our lives, from clothes to footwear, from your bed to the house’s roofing material, from cars through to the construction field [1]. They are in every part of our daily life.
1.2 Types of Polyurethanes, their Properties and Applications
Different types of polyurethanes are available according to their synthetic route and applications. Commonly available polyurethanes are PU foams. Polyurethane foams may be low density flexible foams or low density rigid foams [2]. Low density flexible foams are used for furniture, truck seating, and cushions. The properties required for the usage in such industries are the flexibility, resilience, high mechanical strength, and durability. Rigid foams have high mechanical strength, low heat conduction, low moisture absorption, and low density. They are used as core materials in the manufacturing of thermal insulations in refrigerators and building insulation panels.
Another type is PU elastomers. They have low cost, resistance to high loads, high compression strength, and they can be easily formulated and colored. Polyurethane elastomers are considered as substitutes for plastics and rubbers. They have high abrasion resistance, resistance to solvents and chemicals, high impact strength, and low moisture uptake. These superior mechanical properties make them suitable for the manufacturing of packaging materials, in the health product industry, and the printing industry. They are also used in wheels, rollers, pulleys, shock absorbers, and bushings. Low density elastomers are used in the footwear industry for making shoe soles.
The most important class of polyurethanes are thermoplastic polyurethane. This type of material varies in its starting material and properties. Thermoplastic polyurethanes can be synthesized according to the required properties. They are similar to plastics and they have good elasticity and transparency. Thermoplastic polyurethanes (TPUs) are segmented polyurethanes with alternating hard and soft blocks. The length of the soft and hard blocks can be controlled during the synthesis. They are widely used in the medical equipment, castor wheels, power tools, sports, and the footwear industry. TPUs have high abrasion strength, high chemical and solvent resistance, and resistance to oil and grease.
1.3 Synthesis and Chemistry of Polyurethanes
Polyurethanes are reactive polymers similar to epoxies and polyesters. Polyurethanes are obtained from the reaction between diols and diisocyanates. Diols are systems with two –OH groups and an isocyanate contains –NCO group as the end point. PUs can be synthesized in a single step (the one shot method) by direct mixing of the components or in the prepolymer method. The prepolymer method involves the addition of diol and isocyanate to form the polyurethane prepolymer with –NCO as end groups. This prepolymer is then extended with chain extenders to form polyurethanes. The most commonly used isocyanates for the synthesis of polyurethane are diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) or isophorone diisocyantate (IPDI). Aromatic isocyanates are more reactive than the aliphatic varieties. Polyols used for the synthesis of PUs can be polyether polyols and polyester polyols. The polyether polyols are ethylene glycol, propylene glycol, poly-ethylene propylene oxide and the polyester polyols are condensed products of adipic acid or phthalic acid with 1,4-butane diol, or 1,6-hexane diol. The formation involves a rearrangement step in which the hydrogen from the alcohol to the nitrogen of isocyanate and the oxygen links to the carbon. The simple reaction between –OH and –NCO is represented in the following step
Many side products like urea, allophanate, uric acid, and biuret are possible from the above reaction. A simple representation of the side reactions occurring during the formation of urethane are given in Fig. 1.1.
Figure 1.1 Schematic representation of the side reactions during the reaction between diols and isocyanates.
Polyurethanes normally have a segmented structure. A hard segment derived from the isocyanates and a soft segment from the diols are normally formed. The length and molecular weight of the monomer molecule has a direct influence on the nature of the polyurethane formed. The low molecular weight monomers can produce highly concentrated urethanes and so they will be hard and stiff. On the other hand, long and high weight monomers when combined to form PUs result in a high amount of soft segments. As the concentration of the soft segment increases, the resultant material becomes flexible and elastomeric. The main factor determining the product nature is the NCO–OH ratio. Side reaction inhibitors and the catalyst are unavoidable in the PU synthesis.
A schematic representation of the PU synthesis is given below in Scheme 1.1.
Scheme 1.1 General synthetic route of polyurethane.
One of the special features of polyurethane is that they can be derived from natural sources such as vegetable oils. The synthesis of PU from renewable resources is a method adopted by many researchers. This is a greener approach for the synthesis to be applied for PUs [3,4]. Different types of vegetable oils will give different polyols that can be used for the synthesis of PUs, examples include caster oil, soybean oil, and sunflower oil as source materials. Yagneh and Talemi synthesized and characterized the polyurethanes from caster oil. They found that the synthesized materials are suitable for using as biodegradable implants. They followed the prepolymer method and derived polyol from the caster oil was reacted with isocyanate. The synthetic route is given in Scheme 1.2 [5].
Scheme 1.2 Synthesis of polyurethane from caster oil.
Lignin can be used as a raw material for the synthesis of polyurethanes. Rigid foams, elastomers and sealants can be obtained from the lignin based synthesis. Bio based PU synthesis is economic and promotes green approach of chemistry [6].
Kessler and coworkers [36] compared the –OH values of different vegetable oils and synthesized polyurethane using the polyols derived accordingly. They utilized olive, canola, grape seed, linseed and castor oils. The method was proposed to be solvent- and catalyst free. First they oxidized the triglyceride oils into epoxidized vegetable oil with formic acid and peroxide. Then ring opening polymerization was undertaken with caster oil (Scheme 1.3).
Scheme 1.3 Preparation of vegetable oil based polyols.
Polyurethanes involve toxic isocyanates and phosgene. Avoiding the toxicity in PU synthesis is an important concern for the synthetic chemistry. This is the role of nonisocyante routes which is applied nowadays to make polyurethanes. Nonisocyante PUs can be synthesized from amines and diols or using cyclo carbonates [7]. In their review work, Cramail et al. explained the normal synthesis of PU and the nonisocyanate method known as transurethanization. Here the alcohol is mixed with carbamate and results in polyurethanes with similar properties that are obtained via the isocyanate method [8].
The nonisocyante polyurethanes possess higher chemical resistance and lower permeability than the conventional polyurethanes [9,10] (Scheme 1.4).
Scheme 1.4 Three main steps of PU synthesis by a trans urethane polymerization.
1.4 Structural Analysis of Polyurethanes
Thermoplastic polyurethanes have a segmented structure. Segmented polyurethanes are also considered as block copolymers of type (AB)n with alternating soft (A) and hard (B) segments. The specific segments have specific applications and properties. The detrimental factor in the PU applications are the length of each segment. The hard segments (HS) appear as dispersed in a matrix of soft segments (SS). A schematic representation of the segmented polyurethane is given in Scheme 1.5 [11].
Scheme 1.5 Segmented polyurethane.
The hard segments are normally aligned and induce crystallinity to the segmented PUs. Hence, some PUs are semicrystalline and have improved properties. The crystalline structure is observed at lower temperatures. At high temperatures, the crystallites melt and thus the structural changes with the application of temperature can be studied by Differential Scanning Calorimetry (DSC) and X-Ray diffraction (XRD) [12,13] (see Fig. 1.2).
Figure 1.2 The segmented structure of polyurethane.
1.5 Phase Separation and Miscibility
The segmented polyurethanes are of importance due their special behavior of phase separation. The two segments, hard and soft, have high interphase adhesion, but they do not fail at the interphase. Polyurethanes will tend to phase separate because of the incompatibility between the soft and hard segments [14,15]. The hard segments normally act as crosslinks in the matrix [16]. The enhanced properties of PUs are considered as a result of this phase separation. Petrovic and Ferguson [17] explained the phenomena of phase separation in polyurethanes and the thermodynamics of miscibility and phase separation. They considered the PU system to be similar to a polymer blend system, where the resultant blend is an average of the properties of the two polymers. In the case of PUs, the property of the material is the added sum of the hard segments and the soft segments [17]. Phase separation phenomena in segmented PUs depends mainly on the length of the hard and soft segments. If the soft segments are too long then they will phase separate and if they are too short, then the possibility of phase separation is decreased [18]. Phase separation process in PUs are affected by the hydrogen bonding interactions between urethane linkages, the reaction conditions during synthesis, the length of hard domains, and the temperature. The phase separation process is determined by the Differential Scanning Calorimentry [19], small angles X-ray scattering (SAXS) [20] and morphological analysis. Li and coworkers considerd the phase separation in segmented polyurethanes with the help of the SAXS technique. They concluded that the kinetics factor could control whether it was phase mixed or phase separated [21,22]. The DSC measurements are based on the fact that the two segments have different Tg and the variation in the glass transition temperature is useful in the study of phase separation in PUs. The hydrogen bonding interactions inside the polyurethane chains also plays a role in the phase separation process [23]. The variation in the temperature is a governing factor in the phase separation process. The separated structure at room temperature is extremely different from that at high temperature. A schematic representation of the separated structure at different temperatures is given in Fig.
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