Bio-based polyamide

Of course, as we will see with recycled and bio-based polyamide blends [LOU 13], it is wise to associate them both. It is also necessary to develop recyclable bio-based materials [MUL 13] and develop the use of natural additives [AMB 11]. 

Table 10.1 Selection of properties for typical base petro-based and bio-based polyamides.

It is conceivable that the bio-based polyamides might also find many suitable appUcations in the broad area of automotive and tmck parts, but due to their current price situation and low capacities it is highly unlikely that this will be the dominant segment. As seen in Table 10.1, the bio-based polyamides have a different set of properties compared to the more price sensitive short-chain polyamides. To gain market entrance, it would be wise to focus on appUcation... 

As a final note, it is also conceivable that several petro-based and bio-based polyamides will be copolymerized or blended to tailor to meet the needs of certain application areas. In essence, this would create an ideal combination of properties to facilitate an ideal price-to-performance ratio. It should then be mentioned that this will further expand the product portfolio and make listed comparisons, such as in Table 10.1, nearly impossible to construct. The future of biopolyamides may be in consolidation and a clear-cut focus on certain defined applications areas demanding their specific properties. The actual development remains to be seen. 

Bio does not necessarily have to denote low quality or inferior let alone biodegradable. As mentioned in section 10.2.1, polyamides are true high performance polymers, yet seeing that only 5% of the current biopolymer market is served by PA-types it may take a while to modify the public perception and association. In this respect, the title of this chapter has been well chosen. Furthermore, several of the main bio-based polyamide producers have opted to use the trade names originally deemed for their main petro-based polyamides to uphold the notion of high performance, for example Arkema with Rilsan or Evonik with Vestamid (see Table 10.2). 

Influence of Ester Groups on the Physical Properties of Polyolefins Bio-Based Polyamides... 

Figure 12 (A) Variable-temperature solid-state C H CP/MAS NMR spectra of a bio-based polyamide synthesized from sebacic acid and diaminoisosorbide (DAIS). (B) 2D FSLG-HETCOR spectrum acquired using a CP time of 2.0 ms. (C) 2D...

Table 13.1 Material properties of petroleum-based polyamides PA6 and PA6.6 and fully or partially bio-based polyamides PA6.10, PA10.10, PA4.10, and PA5.10.

Figure 13.3 Workflow developed by Kind et al. for manufacturing of 100% bio-based polyamide PA5.10 comprising (i) tailoring of C. glutamicum for DAP production through systems metabolic engineering, (ii) medium...

Bio-based and recycled polymers often have short-lifecycles compared to oil-based virgin resins. We studied bio-based (PAX) and recycled (PA6) polyamide (PA) blends [LOU 13]. Scanning electron microscopy (Figure 12.4) shows that the formulations are composed of 75% PA6 and 25% PAX by mass (denoted PA6/PAX (25/75)) and PAX nodules appear in the PA6 matrix. To refine the morphology and improve PA6/PAX interfaces, we conducted reactive compatibilization to couple the... 

The book addresses the most important biopolymer classes like polysaccharides, lignin, proteins and polyhydroxyalkanoates as raw materials for bio-based plastics, as well as materials derived from bio-based monomers like lipids, poly(lactic acid), polyesters, polyamides and polyolefines. Additional chapters on general topics - the market and availability of renewable raw materials, the importance of bio-based content and the issue of biodegradability - will provide important information related to all bio-based polymer classes. 

Although, the lactams are limited to certain geometrically stable ring structures, in theory nearly any combination of an amide and carboxylic acid monomer could create a polyamide. In practice, however, only several major petro-based and bio-based types have been established. 

The collective value and supply chain of bio-based products is relatively new. While some bio-polyamides have been on the market longer than others (read PAl 1 vs. PAIOT), they are still novel polymers with plenty of room for improvement. 

As a final word, bio-polyamides are a clear example showing that bio-based and high performance can correiate and, considering that the original definition of sustainable is something that lasts , bio-polyamides are truly sustainable. 

More recently, some other monomers have been studied. The attraction of production of well-known materials from renewable feedstock led to studies of the use of ethanol for the production of bio-based polyethylene (PE), of caprolactam and muconic acid for the production of polyamides (PA) and of isobutylene for the synthesis of polyisobutylene. 

Sebastian Munoz-Guerra completed his Ph.D in Organic Chemistry in 1974 at the University of Seville. After postdoctoral work on crystal structure and morphology of non-conventional nylons, he initiated research on synthesis and characterization of bio-based polymers and copolymers. Since 1987, he is full Professor in Chemical Engineering at the Technical University of Catalonia in Barcelona. His current research is focussed on the development of polyesters, polyamides and polyurethanes derived from carbohydrates with special attention paid to industrial aromatic polyesters, as well as on modification of microbial biopolymers with therapeutic interest. He has authored more than 200 peer reviewed papers and several book chapters, and has been granted more than 15 patents on these issues. 

Cadaverine (diaminopentane, DAP), a carbon-5 aliphatic metabolite, is a minor member of the biogenic polyamine family. It owes its trivial name to its first discovery in 1885 during systematic investigation of the putrefaction process of human cadavers [52]. In contrast to DAB, there is no efficient petrochemical production route available, which for a long time hampered its industrial application in the polymer industry. However, several bio-based production processes have meanwhile been developed for DAP production from renewable resources [6, 12, 15-17, 53]. Only recently, Cathay introduced the fully biobased polyamide PA5.10 Terryl , which entered the market in 2015. While the proprietary production process relies on biocatalytic conversion of the rather high-priced fine-chemical lysine, other attempts aim at a fully novo biosynthesis with streamlined cell factories for the direct fermentative production of DAP from cheap conventional fermentation feedstock. For establishing a one-step fermentation process for DAP, the industrial lysine producers E. coli and C. glutamicum were therefore the ideal metabolic chassis. 

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