Starch-amine derivatives

Cationic Starches. The two general categories of commercial cationic starches are tertiary and quaternary aminoalkyl ethers. Tertiary aminoalkyl ethers are prepared by treating an alkaline starch dispersion with a tertiary amine containing a P-halogenated alkyl, 3-chloto-2-hydtoxyptopyl radical, or a 2,3-epoxypropyl group. Under these reaction conditions, starch ethers are formed that contain tertiary amine free bases. Treatment with acid easily produces the cationic form. Amines used in this reaction include 2-dimethylaminoethyl chloride, 2-diethylaminoethyl chloride, and A/-(2,3-epoxypropyl) diethylamine. Commercial preparation of low DS derivatives employ reaction times of 6—12 h at 40—45°C for complete reaction. The final product is filtered, washed, and dried. 

Some commercial durable antistatic finishes have been Hsted in Table 3 (98). Early patents suggest that amino resins (qv) can impart both antisHp and antistatic properties to nylon, acryUc, and polyester fabrics. CycHc polyurethanes, water-soluble amine salts cross-linked with styrene, and water-soluble amine salts of sulfonated polystyrene have been claimed to confer durable antistatic protection. Later patents included dibydroxyethyl sulfone [2580-77-0] hydroxyalkylated cellulose or starch, poly(vinyl alcohol) [9002-86-2] cross-linked with dimethylolethylene urea, chlorotria2ine derivatives, and epoxy-based products. Other patents claim the use of various acryUc polymers and copolymers. Essentially, durable antistats are polyelectrolytes, and the majority of usehil products involve variations of cross-linked polyamines containing polyethoxy segments (92,99—101). 

Starch is the most widely used dry strength additive and is normally made in a cationic form by introducing a reactive monomeric or polymeric tertiary amine or quaternary ammonium derivative into the molecule. The most commonly used reagent for tertiary amino starch is 2-chloroethyldiethylammonium chloride, and for quaternary starch is 2,3-epoxypropyltrimethylammonium chloride (Figure 7.10). 

AGs and APGs are produced completely with renewable feedstocks such as glucose and fatty alcohols derived from starch and palm kernel oil [34]. AGs, which are mainly the two homologues C12- and C14-1V-methyl glucamide, are manufactured by reductive amination of glucose followed by acylation with fatty acid derivatives [35],... 

This method was reported before as a convenient way to couple drugs to dextran and starch (7). For the attachment of alcohols this method is obviously only practical when using the tri-ester derivatives in order to avoid intra- or inter-molecular reactions during the subsequent coupling procedures. However also with amine type drugs similar competitive side reaction may occur as will be illustrated. 

Renewable raw materials can contribute to the sustainability of chemical products in two ways (i) by developing greener, biomass-derived products which replace existing oil-based products, e.g. a biodegradable plastic, and (ii) greener processes for the manufacture of existing chemicals from biomass instead of from fossil feedstocks. These conversion processes should, of course, be catalytic in order to maximize atom efficiencies and minimize waste (E factors) but they could be chemo- or biocatalytic, e.g. fermentation [3-5]. Even the chemocatalysts themselves can be derived from biomass, e.g. expanded com starches modified with surface S03H or amine moieties can be used as recyclable solid acid or base catalysts, respectively [6]. 

Aminated starches have been further converted. For example, dimethyl-aminoethyl starch could be converted into glycosides by alcoholysis,2442 phosphorylated with sodium dihydrogenphosphate, and oxidized with hydrogen peroxide to carboxyl derivatives.520 Additional information on this subject can be found in Section VII. 2-Hydroxypropyltrimethylammonium chloride starch has been crosslinked with epichlorohydrin.2443 In contrast to animation, which requires basic solutions, phosphorylation occurs at pH 6.2444... 

Starch dialdehyde condenses readily with amino amides2624 and diamines,2625 and forms oximes with hydroxylamine.2626 The reaction of starch dialdehyde with isoniazid, 4 -formacelanilide thiosemicarbazone, 4 - amin o b e n z a I de h y de thiosemicarbazone or thiosemicarbazone, produced the corresponding condensation products.613-615 617 2627-2629 Hydrazones were readily formed when hydrazine and its derivatives were blended with starch dialdehyde and acidified with acetic acid2543,2630 or simply on heating the reaction mixture.2631 Condensation of starch... 

Poly(amino acids)2892 and polypeptides2893 can also be grafted onto starch. Starch was first alkylated in the presence of lithium naphthalene, and then the alkoxy derivatives were reacted with /V-carboxy anhydrides. Poly(amide amines) were produced by reacting amines with dioic acids on starch and then crosslinking with epichlorohydrin or 1,2-dichloroethane 2894 Grafting of starch with a synthetic polymer chain, for instance, polystyryl carboxylate anions prepared by an anionic polymerization, can be carried out on a blend of starch and cellulose functionalized by sulfonation, mesylation, or tosylation. In this manner, cellulose-starch graft copolymers were prepared.2895... 

Protamine. [Nat l. Starch Chem.] Amide-amine fatty deriv. emulsifier, softener, lubricant base. 

Early amphoteric starches contained tertiary aminoethyl ether and phosphate ester groups in which the preferred molar ratios of anionic to cationic groups was from 0.07 to 0.18. Later patents cited phosphate ester and quaternary amine with ratios of 0.014 to 0.92. These derivatives provided synergistic effects and were effective filler retention aids and paper strengthening agents over the pH range from 4.0 to 10.0 [4]. 

To coimter the loss of water dining the process and a significant degradation of the material, to prevent, e.g., the formation of cellular stractures output from an extruder, and to obtain a material with controlled properties, we use a non-volatile plasticizer such as glycerol or other polyols (sorbitol, xylitol, fructose, polyethylene glycol, etc.) [AVE 04a, XIE 12]. Blends of these different polyols are also used [CHI 10b]. Other, notably nitrogenous plasticizers (urea, ammonium derivatives, amines, etc.) can also be used. Plasticized starches are thus created. They are... 

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