Thermoplastic starch biodegradable polymers

Keywords Starch, thermoplastic starch, biodegradable polymers, reactive extrusion... 

Clearly thermoplastic starch based polymers offer a very attractive base for new biodegradable polymers due to their low material cost and ability to be processed on conventional plastic processing equipment. The engineering of more advanced properties into these low cost base materials will continue to be... 

Novamont has been developing thermoplastic starch based polymers since 1990. Mater-Bi polymers are based on thermoplastic starch-blend technologies and product apphcations include biodegradable mulch films and bags, thermoformed packaging products, injection moulded items, personal hygiene items and packaging foam, [http //www.novamont.com/]... 

Biodegradable plastics have been used on an industrial scale since the end of the 1990s when BASF launched Ecoflex . This is a fossil-based, man-made polyester but yet is completely biodegradable due to its chemical structure. This structure is also the reason why Ecoflex combines excellent mechanical properties with the good processability of synthetic thermoplastics. Ecoflex is the preferred blend partner for bio-based and biodegradable polymers, which typically do not exhibit good mechanics and processability for film applications by themselves. Ecoflex therefore is a synthetic polymer that enables the extensive use of renewable raw materials (e.g., starch). 

Eilm products with good mechanical characteristics are only obtained if thermoplastic, plasticized starch has been used. If no plasticizer is used, biodegradable polymers with limited mechanical properties will be obtained. In this case, coextmsion with the base polyester or another polymer is the way to upgrade the mechanical and/or moisture barrier properties (for comparison see Table 6). 

The biodegradable polymer available in the market today in largest amounts is PEA. PEA is a melt-processible thermoplastic polymer based completely on renewable resources. The manufacture of PEA includes one fermentation step followed by several chemical transformations. The typical annually renewable raw material source is com starch, which is broken down to unrefined dextrose. This sugar is then subjected to a fermentative transformation to lactic acid (LA). Direct polycondensation of LA is possible, but usually LA is first chemically converted to lactide, a cyclic dimer of LA, via a PLA prepolymer. Finally, after purification, lactide is subjected to a ring-opening polymerization to yield PLA [13-17]. 

Simmons S, Thomas EL (1995) Structural characteristics of biodegradable thermoplastic starch/poly(ethylene-vinyl alcohol) blends. J Appl Polym Sci 58 2259-2285... 

During the same period, commercialization of thermoplastic starch polymer blends was pursued by Novamont, a division of the Ferruzzi Group of Italy.162-172 Their products, marketed under the trade name Mater-Bi, are typically comprised of at least 60% starch or natural additive and hydrophilic, biodegradable synthetic polymers.64,165 It is stated that these blends form interpenetrated or semi-interpenetrated structures at the molecular level. Properties of typical commercial formulations have properties similar to those in the range of low- and high-density PE. Blends of Mater-Bi products with biodegradable polyesters have been claimed for use as water impervious films.173... 

A wide range of thermoplastic starch compounds have been claimed in recent years. Formulations of thermoplastic starch with linear, biodegradable polyesters, including polycaprolactone and PHBV,174 176 and with polyamides175 have been reported. Laminated structures have been claimed using thermoplastic starch or starch blends as one or more of the layers.175,177,178 The use of polymers latexes as components of thermoplastic starch blends has also been claimed.179 181 Blends with natural polymers are also claimed, including cellulose esters182,183 and pectin.184 A crosslinked thermoplastic material of dialdehyde starch and protein has been reported.185... 

The most relevant achievements in this sector are related to thermoplastic starch polymers resulting from the processing of native starch by chemical, thermal and mechanical means, and to its complexation to other co-polymers. The resulting materials show properties ranging from the flexibility of polyethylene to the rigidity of polystyrene, and can be soluble or insoluble in water as well as insensitive to humidity. Such properties explain the leading position of starch-based materials in the biodegradable polymer field. 

Nodax can be blended with other biodegradable polymers such as polylactic acid and thermoplastic starch for improved processing performance. 

While biodegradable polymers may be similar to petrochemical-based thermoplastics in terms of their structure, their chemical structure imbues them with technical properties that make them perform in different ways. For example, starch blends can produce film with better moisture barrier protection and higher clarity than some conventional plastics. PLA has a high water vapour transmission rate, which is beneficial for fresh food applications where it is important that the water vapour escapes quickly from the packaging. PLA also reduces fogging on the lid of the packaging. 

In recent years starch, the polysaccharide of cereals, legumes and tubers, has acquired relevance as a biodegradable polymer and is becoming increasingly important as an industrial material (Fritz Aichholzer, 1995). Starch is a thermoplastic polymer and it can therefore be extruded or injection moulded (Balta Calleja et al, 1999). It can also be processed by application of pressure and heat. Starch has been used successfully as a matrix in composites of natural fibres (flax, jute, etc.). The use of starch in these composites could be of value in applications such as automobile interiors. An advantage of this biopolymer is that its preparation as well as its destruction do not act negatively upon the environment. A further advantage of starch is its low price as compared with conventional synthetic thermoplastics (PE, PP). 

This article provides a review of thermoplastic starch polymers [unlike polymers with added granular starch] including an introduction to biodegradable polymers and thermoplastic starch polymers a review of thermoplastic starch polymer development a review of reactive modification of thermoplastic starch, examining the structure-property relationships of thermoplastic starch and a review of commercial thermoplastic starch polymer applications. 

Novamont www.novamont.com/ Materbi Thermoplastic starch polymer blends biodegradable mulch films and bags, thermoformed products, injection molded items, and packaging foam... 

Halley P. J. Thermoplastic starch polymers, in Biodegradable polymers for industrial applications R.Smith (ed), Woodhead Pub., London, UK 2005. 

If starch is modified by partially fermenting it, or esterifying or etherification, the resulting material can be extruded by adding plasticizers. Starch-based plastics are readily biodegraded. In most cases, the polymers are also water-soluble. Several suppliers now offer thermoplastic starch. Major markets include soluble films for industrial packaging, films for bags and sacks, and loose fill. 

Thermoplastic starch is also blended with other polymers to improve its properties for particular applications. For example, a bag for collection of household food waste for composting that readily dissolved when it got wet would not function very well In applications such as this, the resins used for blending are also biodegradable, so that they do not interfere with the composting operation. In other cases, starch is blended with nonbiodegradable resins such as polyolefins. 

Chitosan is obtained from the deacetylation of chitin, which is found in marine environments. Because it is insoluble in water, chitosan is dissolved in acidic solutions before being incorporated into biodegradable polymer films. It can also be plasticized with glycerol to obtain a kind of thermoplastic material like, for instance, plasticized starch (Epure, 2011]. 

Natural polymers such as starch and protein are potential alternatives to petroleum-based polymers for a number of applications. Unfortunately, their high solubility in water limit their use for water sensitive applications. To solve this problem thermoplastic starches have been laminated using water-resistant, biodegradable polymers. For example, polylactic acid and P(3HB-co-3HV) were utilised as the outer layers of the stratified polyester/PWS (plasticized wheat starch)/polyester film strucmre in order to improve the mechanical properties and water resistance of PWS which made it useful for food packaging and disposable articles [65]. Moreover, improved physic-chemical interactions between P(3HB-CO-3HV) and wheat straw fibres were achieved with high temperature treatment. It resulted in increased P(3HB-co-3HV) crystallization, increased Young s moduli and lowered values of stress and strain to break than the neat matrix of P(3HB-co-3HV). There was no difference in the biodegradation rate of the polymer [66]. 

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