Quaternary starches

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). 

Follain N., Joly C., Dole R, Roge B., Mathlouthi M., Quaternary starch based blends Influence of a fourth component addition to the starch/water/glycerol system, Carbohydr. Polym., 63, 2006,400-407. 

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. 

Quaternary ammonium alkyl ethers are prepared similarly an alkaline starch is reacted with a quaternary ammonium salt containing a 3-chloto-2-hydtoxyptopyl or 2,3-epoxyptopyl radical. Alternatively, such derivatives can be prepared by simple quaternization of tertiary aminoalkyl ethers by reaction with methyl iodide. Sulfonium (107) and phosphonium (108) starch salts have also been prepared and investigated. Further work has explained the synthesis of diethyl aminoethyl starch (109) as well as the production of cationic starches from the reaction of alkaline starch with... 

Cationic Starches. Commercial cationic starches are starch ethers that contain a tertiary amino or quaternary ammonium group, eg, the diethylaminoethyl ether of starch or the 2-hydroxy-3-(trimethylammonio)propyl ether of starch [9063-45-0], sold as its chloride salt [56780-58-6]. 

Etherification. A mixture of ethylene chlorohydrin ia 30% aqueous NaOH may be added to phenol at 100—110°C to give 2-phenoxyethanol [122-99-6] ia 98% yield (39). A cationic starch ether is made by reaction of a chlorohydfin-quaternary ammonium compound such as... 

Quaternary ammonium compounds (quats) are prepared - by moderate heating of the amine and the alkyl halide in a suitable solvent - as the chlorides or the bromides. Subsequently conversion to the hydroxides may be carried out. Major applications of the quat chlorides are as fabric softeners and as starch cationizing agent. Several bio-active compounds (agrochemicals, pharmaceuticals) possess the quat-structure. Important applications of quat bromides are in phase transfer catalysis and in zeolite synthesis. 

Dry strength additives are usually water soluble, hydrophilic natural or synthetic polymers, the commercially most important of which are starch, natural vegetable gums and polyacrylamides. These polymers are often made in cationic form by the introduction of tertiary or quaternary amino groups into the polymer, and are therefore polyelectrolytes. They are thus also able to function to some extent as drainage and retention aids. 

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... 

Quaternary ammonium starch ethers are prepared by reacting the chlorohydrin form of... 

Cationization and carboxymethylation of starch in an extruder has been reported.45 17 Cationization of potato starch in a twin-screw extruder had an optimum reaction efficiency of 71%. Further work yielded 80% efficiency and products with 0.03-0.10 DS.44 Additional heat treatment of extruded products (made via reaction with quaternary ammonium reagents) with sodium trimetaphosphate or citric acid has improved reaction efficiencies and/or viscosities.48 Dry cationization in the presence of methanol and isopropanol49 or combined with microwave irradiation has also been done.50... 

Various aminoalkyl and alkylaminoalkyl halides react with starch in alkaline media and are readily available by the reaction of epichlorohydrin with primary, secondary, and tertiary amines and even aqueous ammonia. Prior to the reaction with starch, the quaternary ammonium compounds were either decomposed to free amines, or they reacted as amminium compounds to give cationic aminium starches. Cationic starches were produced by the reaction of starch with arylalky-laminoalkyl epoxides. In the presence of formaldehyde, inorganic ammonium salts provided the source of amino groups.1316... 

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