Starch esters applications

Starches have been chemically modified to improve their solution and gelling characteristics for food applications. Common modifications involve the cross linking of the starch chains, formation of esters and ethers, and partial depolymerization. Chemical modifications that have been approved in the United States for food use, involve esterification with acetic anhydride, succinic anhydride, mixed acid anhydrides of acetic and adipic acids, and 1-octenylsuccinic anhydride to give low degrees of substitution (d.s.), such as 0.09 [31]. Phosphate starch esters have been prepared by reaction with phosphorus oxychloride, sodium trimetaphosphate, and sodium tripolyphosphate the maximum phosphate d.s. permitted in the US is 0.002. Starch ethers, approved for food use, have been prepared by reaction with propylene oxide to give hydroxypropyl derivatives [31]. 

Starch, often in its degraded form dextrin, and starch esters have long found application in general emulsion and dispersion technology, mainly in adhesives, construction materials or in pharmaceuticals for example, as aqueous coating material for controlled-release products [106]. 

Most types of Hot melt adhesives used in the mannfacture of laminates and in rapid Packaging industry applications are mineral oil-derived, hydrophobic and essentially non-dispersible, so they cannot be considered as renewable. However, some basic polymers have been prepared over the last decade from vegetable sources, which are renewable, and are adhesive, although these properties have limitations. These include poly(hydro-xybutyrate/hydroxyvalerate) (PHBV), poly(lactide) (which has poor thermal stability), and starch esters. Adhesives based on sulphonated polyesters with polar petroleum waxes have improved adhesion and adequate water dispersibility. In general, however, the perfect adhesive from renewable resources with satisfactory adhesion properties remains to be discovered. 

For these reasons there has been renewed interest in starch-based plastics in recent years. Earlier studies of starch esters and ethers (3-10) indicated that they had inadequate properties in comparison with cellulose derivatives for most applications. More recently, starch graft copolymers (2), starch plastic composites (11,12), and starch itself (13-17) have been proposed as plastic materials. 

Properties of starch esters depend on the type of an esterifying agent applied, conditions of the reaction, and a DS. The esterified starches have found applications in the food industry, papermaking industry, in pharmacy, and have been used for the production of thickening agents and for permanent finishing of fabrics [57],... 

In the past, the study of starch esters and ethers [7-14] was abandoned due to the inadequate properties of these materials in comparison with cellulose derivatives for most applications. 

The viscosity of polymer solutions has been considered theoretically by Flory,130 but although this theory has been applied to cellulose esters,131 no applications have yet been made in the case of the starch components. Theoretical predictions of the effect, on [17], of branching in a polymer molecule have been made,132 and this may be of importance with regard to the viscometric behavior of amylopectin. 

To prepare more hydrophobic starches for specific applications, the partial substitution of starch with acetate, hydroxypropyl, alkylsiliconate or fatty-acid ester groups has been described in the literature. A new route, however, consists of grafting octadienyl chains by butadiene telomerization (Scheme 3.9) [79, 82, 83], The reaction was catalyzed by hydrosoluble palladium-catalytic systems prepared from palladium diacetate and trisodium tris(m-sulfonatophenyl)phosphine (TPPTS). 

Commercially available cationic starches for wet end application are quaternary and tertiary products. These products have been available since about the mid 1950 s and no new basic chemistry has been developed since that time. The development in the late 1940 s and early 1950 s of starch ethers and esters made in the original granule form led to a torrent of starch derivatives for industrial use. Very few of these became commercial. This is possibly because the functions that were required by the industrial and food markets were far... 

In 1833 Braconnot obtained nitric esters of cellulose and starch by acting with nitric acid on plant fibres and starch, at low temperature, hi 1834 Mitscherlich nitrated benzene to nitrobenzene. But it is only since 1842, when Zinin reduced nitrobenzene to aniline, that rapid development of the chemistry of nitro compounds and their application to organic industry has occurred. 

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