Polymers production from vegetable oils

Polymers Unsaturated fatty-acid chains offer opportunities for polymerisation that can be exploited to develop uses in surface coatings and plastics manufacturing. Polyunsaturated fatty acids can be dimerised to produce feedstocks for polyamide resin (nylon) production. Work is also ongoing to develop polyurethanes from vegetable oils through manipulation of functionality in the fatty-acid chains, to produce both rigid foams and elastomers with applications in seals, adhesives and moulded flexible parts (see Chapter 5 for more information). 

Rising prices for safflower and increasingly better water-based paints formulated from petroleum-based polymers rather than vegetable oils quickly cut industrial consumption of safflower oil. PVO attempted to stem this tide by introducing products that combined safflower oil with water emulsion technologies, but it was too late (49-51). 

Generally speaking, numerous synthons can be extracted from biomass. One known example is that of ethylene, produced from the dehydration of ethanol which is a very common product of fermentation. Another example is 1,3-propanediol, which is a monomer used as a building block for the production of polymers such as polyesters and polyurethanes. Several industrial processes have studied its production by fermentation with the aim of producing it directly from inexpensive plant raw materials (starch or sucrose). To synthesize polyamides and polyesters, we also aim to produce a,(o-dicarboxylic acids by the biological conversion of esters from vegetable oils. 

This chapter discusses polymers such as polyamides and polyolefins which are obtained from vegetable oils and will consider the further exploration of vegetable oils for the production of such polymers. 

Specialised polymers, which are mainly used in engineering applications in the automobile, aircraft and machinery industries, are known as engineering polymers. In this group, aliphatic polyamides are the most important and most widely used. A large number of aliphatic polyamides are obtained from vegetable oil-based products. Among these nylon 6,10, nylon 11, nylon 6,9 and poly(amido amine) are very important. One of the most important commercially used polymers, nylon 11, is obtained entirely from castor oU, whereas vegetable oil-derived components are only partly used to prepare other polymers. 

M. Desroches, M. Escouvois, R. Auvergne, S. Caillol, and B. Boutevin, From Vegetable Oils to Polyurethanes Synthetic Routes to Polyols and Main Industrial Products. Polym. Rev. 52, 38-79 (2012). 

As well as the direct production of polymers, vegetable oil derivatives have other uses in the polymer industry, for example as additives. Materials made from vegetable oil have many uses and are used to produce anti-static, slip, and plasticising agents, stabilisers, processing aids and as flame retardants (see Section 2.4.). They can also be incorporated into the manufacture of polyamides, polyesters and polyurethanes. 

The most important monomers for the production of polyolefins, in terms of industrial capacity, are ethylene, propylene and butene, followed by isobutene and 4-methyl-1-pentene. Higher a-olefins, such as 1-hexene, and cyclic monomers, such as norbornene, are used together with the monomers mentioned above, to produce copolymer materials. Another monomer with wide application in the polymer industry is styrene. The main sources presently used and conceivably usable for olefin monomer production are petroleum (see also Chapters 1 and 3), natural gas (largely methane plus some ethane, etc.), coal (a composite of polymerized and cross-linked hydrocarbons containing many impurities), biomass (organic wastes from plants or animals), and vegetable oils (see Chapter 3). 

The Avrami model (19,20) states that in a given system under isothermal conditions at a temperature lower than V. the degree of crystallinity or fractional crystallization (70 as a liinction of time (t) (Fig. 11) is described by Equation 5. Although the theory behind this model was developed for perfect crystalline bodies like most polymers, the Avrami model has been used to describe TAG crystallization in simple and complex models (5,9,13,21,22). Thus, the classical Avrami sigmoidal behavior from an F and crystallization time plot is also observed in TAG crystallization in vegetable oils. This crystallization behavior consists of an induction period for crystallization, followed by an increase of the F value associated with the acceleration in the rate of volume or mass production of crystals, and finally a metastable crystallization plateau is reached (Fig. 11). 

Other modifications of vegetable oils in polymer chemistry include the introduction of alkenyl functions, the study of novel polyesters and polyethers and the synthesis of semi-interpenetrating networks based on castor oil (the triglyceride of ricinoleic acid) [42], and also the production of sebacic acid and 10-undecenoic acid from castor oil [44]. Additionally, the recent application of metathesis reactions to unsaturated fatty acids has opened a novel avenue of exploitation leading to a variety of interesting monomers and polymers, including aliphatic polyesters and polyamides previously derived from petrochemical sources [42, 45]. 

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