Aqueous alcoholic aklaline process for cationization and anioniz

Sugar – starch – and carbohydrates – Processes – Carbohydrate manufacture and refining

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127 32, 127 33, 127 69, 127 70, 106210, 106213, 536106, C08B 3000, C08B 3012, C08B 3100, C08L 300

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058273727

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BRIEF SUMMARY
FIELD OF THE INVENTION

The present invention relates to the production of cationic and amphoteric starches.


BACKGROUND OF THE INVENTION

As described in "Cationic Starches" and "Phosphorylated Starches", Solarek, D. B. in "Modified Starches: Properties and Uses", Wurzburg, O. B. (ed). 1986. CRC Press, Boca Raton, Fla., cationic starches are produced chemically by reacting starch with reagents containing positively charged ions to obtain derivatives such as tertiary amino and quaternary ammonium starch ethers. Cationic starches are particularly useful as wet-end additives, surface sizes and coating binders in papermaking. Cationization is often combined with anionization of the starch to improve the dispersion properties and charge balance of the starch molecules. These amphoteric starch ethers can give equivalent performance to cationic potato starch which is naturally high in phosphate groups.
Several species and biotypes of starch can be cationized effectively to provide a range of functionality for specific requirements in the paper industry. Normal and waxy corn (maize) and potato starches are the most popular starches for commercial cationization. Legume and barley starches are not available commercially in the cationized form but the results of the present investigation suggest that these cationized starches may offer certain advantages from the manufacturing and final usage viewpoint.
Cationized starch is prepared by chemical reaction of starch in a slurry or dry form in batch or continuous reactors at alkaline pH. The slurry system, employing high solids concentrations of 30-45% (Tasset U.S. Pat. No. 4,464,528, issued August, 1984), is the most common system. Unless the cationized starch slurry is used directly for papermaking, it is important that the granular structure of the starch be maintained so that the cationized starch can be recovered readily and completely by filtration or centrifugation. Starch granule swelling and gelatinization are inhibited by adding 10-30% of sodium chloride or sodium sulfate to the alkaline slurry. The chemical reaction must be carried out at no higher temperatures than 60.degree. C. to avoid starch gelatinization. Waxy corn starch is particularly susceptible to gelatinization under alkaline conditions and high levels of gelatinization inhibitors must be used. Therefore, considerable washing of the modified starch is necessary to remove the unreacted residual reagent and gelatinization inhibitor, and effluent recovery costs are high.
The dry processes of starch cationization, as in Roerden et al U.S. Pat. No. 5,241,061, issued August, 1993, also have serious deficiencies, even though they eliminate the need for aqueous treatment and washing of the cationized starch. Reaction rates during dry cationization processes are comparatively low, requiring longer reaction times, and larger concentrations of residual cationic reagent remain in the derivatized starch. In dry cationization, the cationic groups react mainly on the starch granule surfaces and not internally as in aqueous cationization. Because the cationic substituent groups are not uniformly distributed within the starch granules, a portion of the starch, on gelatinization during papermaking, is devoid of functional cationic groups, and remains unabsorbed on the paper and, therefore, increases the eventual effluent load at the paper mill.
There is an urgent need for alternative processes wherein both normal and waxy starches can be uniformly cationized with reasonable reaction times and with minimal effluent treatment costs during manufacturing and utilization.


EXAMPLE OF COMMERCIAL PRACTICE

The current commercial practices for cationization of starch generally follow that of Yook et al. (Effects of cationization on functional properties of pea and corn starches. Yook, C.; Sosulski, F. and Bhirud, P. R. 1994, Starch/Starke, 46, 393-399) who prepared cationic corn and pea starches at four levels of substitution. For each treatment, 50.0 g sodium sulfate and 2.8 g (0.07 moles) NaOH pellets were added to 133

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