Biobased monomers

As is the case for biobased polyolefins, the production of the polymer from the biobased monomer is identical to production of petro-based PET, and the resulting properties are identical (except for the ratio of carbon isotopes, as discussed above). Several routes to terephthalic acid are currently under consideration. They include routes through isobutanol, para-xylene, and muconic acid, derived from various plant sources. 

Some members of the nylon family are also readily produced from biobased monomers. Examples include nylon 6 from biobased caprolactam and nylon 66 from biobased adipic acid. 

Produced by classical chemical synthesis using renewable biobased monomers or mixed sources of biomass and petroleum (i.e., polylactic acid or bio-polyester) ... 

S. Agarwal, Q. Jin, and S. Maji, Biobased polymers from plant-derived tulipalin a, in P.B. Smith and R.A. Gross, eds.. Biobased Monomers, Polymers, and Materials, Vol. 1105 of ACS Symposium Series, pp. 197-212. American Chemical Society, January 2012. 

Producing biobased monomers by fermentation/conventional chemistry followed by polymerization (e.g., polylactic acid, polybutylene succinate and polyethylene) ... 

Biobased polymers or bioplastics, as they are often called, are chemical products made from monomers from plant-based resources. They either have petrochemical equivalents with the same chemical structure and properties against which they have to compete in the market, or can show different structures and performances versus traditional plastics. On a large scale, such biobased monomers are produced in so-called biorefineries. 

The list of monomers described in this chapter is only a 2014 snapshot of technological developments, which, if successful, may lead to commercial opportunities. A similar list of the top 10 biobased monomers in few years will probably look completely different. 

Novel aromatic-aliphatic biobased polyesters showing thermotropic behavior in the melt have been presented, incorporating different biobased monomers such as 2,5-furandicarbo)ylic acid (2,5-FDCA), suberic acid (SuA), and vanillic acid (VA) in thermotropic L.C. polymers (TLCPs). The chemical structures, molecular weights, phase transitions, thermal behavior, and mechanical performance of the synthesized polymers are studied using polarization optical microscopy, WAXD, DSC, TGA, DMTA, SS NMR spectroscopy, rheology, and tensile tests. These materials show a low temperature transition from the crystalline to the nematic phase, and stable nematic phases up to 300 °C and higher. ... 

Coca-Cola (2011) The Coca-Cola company announces partnerships to develop commercial solutions for plastic bottles made entirely from plants. Press release, de Jong E, Dam MA, Sipos LG, Gmter G-JM (2012) Furandicarboxylic acid (FDCA), a versatile building block for a very interesting class of polyesters, hi Smith PB, Gross RA (eds) Biobased monomers, polymers, and materials, vol 1105. American Chemical Society, Washington, DC, pp 1-13... 

The selection of an appropriate polymer matrix for nanocomposites is especially crucial in terms of the design and development of medical implants and products. Biodegradable polymer matrices can be either of natural or synthetic origin. As shown in Fig. 21.24. Natural, biobased polymers can be dived into three groups directty produced by genetically modified organisms, synthesized from biobased monomers or directly from biomass. Polymers synthesized from biobased monomers are often regarded as synthetic [36,39,40]. 

Esters represent an important class of chemical compounds with applications as solvents, plasticizers, flavors and fragrances, pesticides, medicinals, surfactants, chemical intermediates, and monomers for resins. Recently, esters of amino acids have attracted attention regarding their use as biobased surfactants with excellent adsorption and aggregation properties, low toxicity, and broad biological activity. 

Heterogeneous catalysts, particularly zeolites, have been found suitable for performing transformations of biomass carbohydrates for the production of fine and specialty chemicals.123 From these catalytic routes, the hydrolysis of abundant biomass saccharides, such as cellulose or sucrose, is of particular interest. The latter disaccharide constitutes one of the main renewable raw materials employed for the production of biobased products, notably food additives and pharmaceuticals.124 Hydrolysis of sucrose leads to a 1 1 mixture of glucose and fructose, termed invert sugar and, depending on the reaction conditions, the subsequent formation of 5-hydroxymethylfurfural (HMF) as a by-product resulting from dehydration of fructose. HMF is a versatile intermediate used in industry, and can be derivatized to yield a number of polymerizable furanoid monomers. In particular, HMF has been used in the manufacture of special phenolic resins.125... 

Metabolic pathway engineering [125] is used to optimise the production of the required product based on the amount of substrate (usually biomass-derived) consumed. A so-called biobased economy is envisaged in which commodity chemicals (including biofuels), specialty chemicals such as vitamins, flavors and fragrances and industrial monomers will be produced in biorefineries (see Chapter 8 for a more detailed discussion). 

The language used to describe these new (or sometimes old ) materials can be confusing, and too often is misused. One particularly problematic term is bioplastics. One common definition for bioplastics is plastics that are either biodegradable or made from renewable sources a clear recipe for confusion. We will not use this term. Rather, we will use the term biobased plastics to refer to plastics made from biological sources (typically plants). The plastics may be made directly by biological organisms (e.g., polyhydroxyalkanoates) or by chemical polymerization of monomers made from such sources (e.g., polylactide). Plastics may also be partially biobased (such as the CocaCola PlantBottle made from PET that is partially biobased). 

There continue to be efforts to develop additional biobased plastics. Generally these are produced by conventional polymerization methods from biologically derived monomers (usually produced by fermentation from starch, sugar, or cellulose). And, the resulting plastics are most often not biodegradable. 

Biodegradable plastics based on lactic acid have been available on a small scale for many years. They have been used In applications such as medical implants, but their high price was a deterrent to widespread use in lower value applications such as packaging. However, new technologies for production of lactide monomers greatly lowered costs, making the polymers much more competitive. Generally, the lactic acid is obtained from corn or other biobased materials by a fermentation process, and then chemical synthesis is used to produce the polymer from the lactic acid or lactide monomers. 

Polylactic acid (PEA) is probably the best-known biobased polymer. It is made from glucose by fermentation to its monomer lactic acid. Two molecules of lactic acid are then condensed into the dimer lactide, which is subsequently ring-opened and polymerized to PLA in the presence of a catalyst. 

Professor Galen J. Snppes, University of Missonri-Colnmbia Biobased Propylene Glycol and Monomers from Natural Glycerin... 

Lignin, suberin, vegetable oUs, tannins, natural monomers like terpenes, and monomers derived from sugars are typically natural precursors for biobased industrial polymers. Glycerol and ethanol also play a potential role as future precursors to monomers (17). 

Monomers containing the 1,4-cyclohexylene unit are interesting because they are potentially biobased and rigid enough to improve the glass transition temperature as well as the melting temperature (2). The preparation of poly(l,4-cyclohexylenedimethylene adipate) has been described. 

Polybutylene Succinate (PBS). Manufacturers of polybutylene succinate, produced from polymerization of succinic acid and 1,4-butanediol, include Showa Highpoly-mer, which produces Bionolle polymers SK Polymers, which makes SkyGreen BDP and Mitsubishi Chemical. Normally, the source of both monomers is maleic anhydride. However, Mitsubishi is working with Ajinomoto to produce succinic acid by fermentation of sugar and starch, providing a biodegradable polymer that is partly biobased. ... 

As new markets develop for the monomer, lactic acid, through, for example, its conversion to ethyl lactate for use as a biobased solvent, the cost of PLA may be reduced. 

The natural resins present in native guayule have been extensively studied and include mono-, sesqui-, di-, and triterpene groups, as well as other secondary metabolites (108). Unfractionated guayule resin has shown considerable promise in the areas of wood preservation (in marine and terrestrial environments) (129) and insect antifeedents (termite resistance) (130-132). These resins also show promise as a biobased renewable replacement for petroleum-based monomers and oligomers in adhesives and coatings. Additional profitable uses for the resins include a natural, low toxicity replacement for creosote in wood treatment and for prevention of termite attack. Resin/lignin products, such as additives for phenol formaldehyde resins, may also prove possible. 

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