Polymers from natural products

The first alkene polymer to be used in society was polyisoprene, a natural product extracted from the sap of rubber trees. See our Box for a description of the history of rubber. The monomer from which this polymer is constructed... 

The terpenoids form a large and structurally diverse family of natural products derived from C5 isoprene units (Figure 5.1) joined in a head-to-tail fashion. Typical structures contain carbon skeletons represented by (Cs) , and are classified as hemiterpenes (C5), monoterpenes (C10), sesquiterpenes (C15), diterpenes (C2o), sesterterpenes (C25), triterpenes (C30) and tetraterpenes (C40) (Figure 5.2). Higher polymers are encountered in materials such as rubber. Isoprene itself (Figure 5.1) had been characterized as a decomposition product from various natural cyclic hydrocarbons, and was suggested as the fundamental building block for these compounds, also referred to as isoprenoids . Isoprene is produced naturally but is not involved in the formation of... 

Enzymatic development of functional polymers for application as coating or adhesive materials, for example, has attracted much scientific interest over the years. A number of natural products ranging from plant to animal polymers are being actively investigated. In this section, the ability of heme peroxidases to mediate the production of such polymers is revised. 

Several natural materials (waxes, clays, and asphalts) have rheological properties similar to synthetic products, but because they are not polymeric, are not considered true plastics. Certain proteins (casein, zein) are natural high polymers from which plastics are made (buttons and other small items), but they are of decreasing importance. 

A potentially important industrial extension of the production of naturally biodegradable polymers from renewable resources is the utilisation of biological processes to synthesise biodegradable polymers. 

Polymers obtained from natural products or from their immediate derivatives such as vegetable oil, modified epoxidised oils, transesterified oils, heated oil, monoglyceride and diethanol amide or fatty acids of vegetable oils, cashew nut seed liquid (CNSL) and derivatised polymers, are bioderived polymers. " The details of vegetable oil-based polymers are the subject matter of this book and hence are discussed in detail in subsequent chapters. 

Dr. B.R. Ambedkar National Institute of Technology -Jalandhar. Seven students have completed their Ph.D. degree under his supervision. He has a wide experience in the field of natural products, polymers composites, hydrogels, removal of toxic heavy metal ions from waste water, removal of colloidal particles, sustained drug delivery, controlled release of insecticides/pesticides, etc. He has more than 80 research papers in various reputed international journals. He has more than 60 research papers in the proceedings of the international conferences and... 

Green polymer synthesis—the preparation of polymers by environmentally friendly methods using starting materials that are not derived from petroleum—is an active area of research. One example is the polymerization of tulipalin A, a natural product derived from tulips, to afford polytulipalin. Polytulipalin has properties similar to some petroleum-derived polymers, but its availability from a natural source has made It a possible attractive alternative to these polymers. Polymerization occurs in the presence of a strong base (B ), and each new C-C bond in polytulipalin is formed by a Michael reaction. Draw a stepwise mechanism for the formation of one C-C bond in polytulipalin. (See Section 30.8 for other aspects of green polymer chemistry.)... 

Cellophane was a common material used in film for various packaging applications in the 1950s and remains to some extent in use today. Cellophane is produced from raw cellulose, which is a natural product derived from plant matter. The structure of cellophane, which is a biodegradable polymer, is shown in Figure 5.2. 

Emulsion Adhesives. The most widely used emulsion-based adhesive is that based upon poly(vinyl acetate)—poly(vinyl alcohol) copolymers formed by free-radical polymerization in an emulsion system. Poly(vinyl alcohol) is typically formed by hydrolysis of the poly(vinyl acetate). The properties of the emulsion are derived from the polymer employed in the polymerization as weU as from the system used to emulsify the polymer in water. The emulsion is stabilized by a combination of a surfactant plus a coUoid protection system. The protective coUoids are similar to those used paint (qv) to stabilize latex. For poly(vinyl acetate), the protective coUoids are isolated from natural gums and ceUulosic resins (carboxymethylceUulose or hydroxyethjdceUulose). The hydroHzed polymer may also be used. The physical properties of the poly(vinyl acetate) polymer can be modified by changing the co-monomer used in the polymerization. Any material which is free-radically active and participates in an emulsion polymerization can be employed. Plasticizers (qv), tackifiers, viscosity modifiers, solvents (added to coalesce the emulsion particles), fillers, humectants, and other materials are often added to the adhesive to meet specifications for the intended appHcation. Because the presence of foam in the bond line could decrease performance of the adhesion joint, agents that control the amount of air entrapped in an adhesive bond must be added. Biocides are also necessary many of the materials that are used to stabilize poly(vinyl acetate) emulsions are natural products. Poly(vinyl acetate) adhesives known as "white glue" or "carpenter s glue" are available under a number of different trade names. AppHcations are found mosdy in the area of adhesion to paper and wood (see Vinyl polymers). 

Other typical pyrotechnic fuels include charcoal, sulfur, boron, siUcon, and synthetic polymers such as poly(vinyl alcohol) and poly(vinyl chloride). Extensive use has been made of natural products such as starches and gums, and the use of these materials continues to be substantial in the fireworks industry. MiUtary pyrotechnics have moved away from the use of natural products due to the inherent variabiUty in these materials depending on climatic conditions during the growth of the plants from which the compounds are derived. 

Adsorption and Desorption Adsorbents may be used to recover solutes from supercritical fluid extracts for example, activated carbon and polymeric sorbents may be used to recover caffeine from CO9. This approach may be used to improve the selectivity of a supercritical fluid extraction process. SCF extraction may be used to regenerate adsorbents such as activated carbon and to remove contaminants from soil. In many cases the chemisorption is sufficiently strong that regeneration with CO9 is limited, even if the pure solute is quite soluble in CO9. In some cases a cosolvent can be added to the SCF to displace the sorbate from the sorbent. Another approach is to use water at elevated or even supercritical temperatures to facilitate desorption. Many of the principles for desorption are also relevant to extraction of substances from other substrates such as natural products and polymers. 

Most toxicity problems associated with the finished product arise from the nature of the additives and seldom from the polymer. Mention should, however, be made of poly(vinyl carbazole) and the polychloroacrylates which, when monomer is present, can cause unpleasant effects, whilst in the 1970s there arose considerable discussion on possible links between vinyl chloride and a rare form of cancer known as angiosarcoma of the liver. 

We have seen that physical chemistry evolved from a deep dissatisfaction in the minds of a few pioneers with the current state of chemistry as a whole one could say that its emergence was research-driven and spread across the world by hordes of new Ph.Ds. Chemical engineering was driven by industrial needs and the corresponding changes that were required in undergraduate education. Polymer science started from a wish to understand certain natural products and moved by... 

Another natural polymer that needs a fresh look into its structure and properties is bitumen [123], also called asphaltines, that are used in highway construction. Although a petroleum by-product, it is a naturally existing polymer. It primarily consists of polynuclear aromatic and cyclocaliphatic ring systems and possesses a lamellar-type structure. It is a potential material that requires more study, and high-performance materials such as liquid crystalline polymer (LCP) could be made from it. 

Radical polymerization is often the preferred mechanism for forming polymers and most commercial polymer materials involve radical chemistry at some stage of their production cycle. From both economic and practical viewpoints, the advantages of radical over other forms of polymerization arc many (Chapter 1). However, one of the often-cited "problems" with radical polymerization is a perceived lack of control over the process the inability to precisely control molecular weight and distribution, limited capacity to make complex architectures and the range of undefined defect structures and other forms of "structure irregularity" that may be present in polymers prepared by this mechanism. Much research has been directed at providing answers for problems of this nature. In this, and in the subsequent chapter, we detail the current status of the efforts to redress these issues. In this chapter, wc focus on how to achieve control by appropriate selection of the reaction conditions in conventional radical polymerization. 

Allylic alcohols can be converted to epoxy-alcohols with tert-butylhydroperoxide on molecular sieves, or with peroxy acids. Epoxidation of allylic alcohols can also be done with high enantioselectivity. In the Sharpless asymmetric epoxidation,allylic alcohols are converted to optically active epoxides in better than 90% ee, by treatment with r-BuOOH, titanium tetraisopropoxide and optically active diethyl tartrate. The Ti(OCHMe2)4 and diethyl tartrate can be present in catalytic amounts (15-lOmol %) if molecular sieves are present. Polymer-supported catalysts have also been reported. Since both (-t-) and ( —) diethyl tartrate are readily available, and the reaction is stereospecific, either enantiomer of the product can be prepared. The method has been successful for a wide range of primary allylic alcohols, where the double bond is mono-, di-, tri-, and tetrasubstituted. This procedure, in which an optically active catalyst is used to induce asymmetry, has proved to be one of the most important methods of asymmetric synthesis, and has been used to prepare a large number of optically active natural products and other compounds. The mechanism of the Sharpless epoxidation is believed to involve attack on the substrate by a compound formed from the titanium alkoxide and the diethyl tartrate to produce a complex that also contains the substrate and the r-BuOOH. ... 

Polymers are very large organic molecules that are either made synthetically or are of natural origin, and find use as plastics, rubber, fibers, and coatings. Polymers were first produced commercially in 1860 by modification of cellulose from wood or cotton, followed by a fully synthetic product made from phenol and formaldehyde in 1910. 

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