Starch alcohols

Chemistry (Theoretical and Applied).—Air. Water. Chemical theory. Acids, alkalies and salts. Carbon and its oxides fuels. Soaps. Textile fabrics. Water softeners. Sugars, starch, alcohol, acetic acid. Proteins. Fats. Yitamines. Yeasts, moulds and bacteria. Study of certain foods. Preservation and sterilisation of food stuffs. The practical work will be partly illustrative of the lectures, and partly experimental craft work, i.e. —... 

Previous reports on starch-alcohol interactions assumed that only physical sorption is involved, despite observations of the irreproducibility of successive adsorption-desorption isotherms for starch-methanol and starch-ethanol systems. This irreproducibility was assumed to be the result of swelling.354... 

According to Hollo et al.,709 the low stability of starch-alcohol complexes (lower than that of the starch-iodine complex) is caused by the relatively small amount of space inside the amylose helix that is available for the hydrophobic moiety of the alcohol. The data in Table XXX appear to confirm this assumption and indicate iodine sorption amounts by starch complexes with subsequent members of the homologous series of alcohols. With the exception of ferf-butanol, the iodine uptake decreases as the alcohol inside of the helix becomes more bulky. 

Conditions for the formation of potato starch-alcohol complexes do not follow predictable trends. For example, all complexes are formed more readily from air-dried starch rather than from oven-dried starch. Only the starch-methanol complex favors room temperature for its formation the other alcohols require elevated temperatures for effective complexations (see Table XXXI).659,681 682 In contrast, moisture inhibits the formation of the starch-(-)-menthol complex, which is characterized as an interchain complex.710 The Scatchard binding parameters show that (-)-menthol and 1-hexanol adsorb on starch by only one mode, whereas 1-octanol and 1-decanol adsorb in two modes.656 The results for the latter two alcohols indicate that the helices are not fully filled before the second mode of complexation starts. Temperatures of the formation of starch-alcohol complexes likewise do not follow any clear relationship.673,680 Bushuk and Winkler687 reported that the amount of guest molecules (HzO, MeOH,... 

Binding parameters and X-ray diffraction patterns of the complex of starch with 1-decanal do not differ significantly from corresponding analyses performed using 1-decanol.656,679 The temperatures of formation of the aldehyde complexes are likewise close to those for relevant starch-alcohol complexes.673,680 Analysis of the binding sites of the complex suggests that both amylose and amylopectin are involved in complexation, but these complexes are rather weak.717... 

Approximately 98% of US bioethanol is based on com (Zea Mays), a raw starchy material produced in high quantities in that country (14,216 MkT in 2014). Total domestic use of corn in US was 11,883 MkT in the same year. From that amount, 5208 MkT of com were used for ethanol production, 5315 MkT for feed and residual use purposes, while the rest was transformed into high-fructose com symp, sugars (glucose and dextrose), starch, alcohol for beverages and manufacturing, seeds, cereals, and other products (Service, 2015). 

Molisch s Test. Dissolve about 01 g. of the carbohydrate in z ml. of water (for starch use 2 ml. of starch solution ), add 2-3 drops of a 1 % alcoholic solution of i-naphthol (ignoring traces of the latter precipitated by the water) and then carefully pour 2 ml. of cone. H2SO4 down the side of the test-tube so that it forms a heavy layer at the bottom. A deep violet coloration is produced where the liquids meet. This coloration is due apparently to the formation of an unstable condensation product of i-naphthol with furfural (an aldehyde produced by the dehydration of the carbohydrate). 

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

Recovery of the wopropyl alcohol. It is not usually economical to recover the isopropyl alcohol because of its lo v cost. However, if the alcohol is to be recovered, great care must be exercised particularly if it has been allowed to stand for several days peroxides are readily formed in the impure acetone - isopropyl alcohol mixtures. Test first for peroxides by adding 0-6 ml. of the isopropyl alcohol to 1 ml. of 10 per cent, potassium iodide solution acidified with 0-6 ml. of dilute (1 5) hydrochloric acid and mixed with a few drops of starch solution if a blue (or blue-black) coloration appears in one minute, the test is positive. One convenient method of removing the peroxides is to reflux each one litre of recovered isopropyl alcohol with 10-15 g. of solid stannous chloride for half an hour. Test for peroxides with a portion of the cooled solution if iodine is liberated, add further 5 g. portions of stannous chloride followed by refluxing for half-hour periods until the test is negative. Then add about 200 g. of quicklime, reflux for 4 hours, and distil (Fig. II, 47, 2) discard the first portion of the distillate until the test for acetone is negative (Crotyl Alcohol, Note 1). Peroxides generally redevelop in tliis purified isopropyl alcohol in several days. 

Iodine compounds are important in organic chemistry and very useful in medicine. Iodides, and thyroxine which contains iodine, are used internally in medicine, and as a solution of KI and iodine in alcohol is used for external wounds. Potassium iodide finds use in photography. The deep blue color with starch solution is characteristic of the free element. 

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

Water-Soluble Films. Water-soluble films can be produced from such polymers as poly(vinyl alcohol) (PVOH), methylceUulose, poly(ethylene oxide), or starch (qv) (see Cellulose ethers Polyethers Vinyl polymers). Water-soluble films are used for packaging and dispensing portions of detergents, bleaches, and dyes. A principal market is disposable laundry bags for hospital use. Disposal packaging for herbicides and insecticides is an emerging use. 

Polymers. AH nitro alcohols are sources of formaldehyde for cross-linking in polymers of urea, melamine, phenols, resorcinol, etc (see Amino RESINS AND PLASTICS). Nitrodiols and 2-hydroxymethyl-2-nitro-l,3-propanediol can be used as polyols to form polyester or polyurethane products (see Polyesters Urethane polymers). 2-Methyl-2-nitro-l-propanol is used in tires to promote the adhesion of mbber to tire cord (qv). Nitro alcohols are used as hardening agents in photographic processes, and 2-hydroxymethyl-2-nitro-l,3-propanediol is a cross-linking agent for starch adhesives, polyamides, urea resins, or wool, and in tanning operations (17—25). Wrinkle-resistant fabric with reduced free formaldehyde content is obtained by treatment with... 

The paster is a nonheated operation. The most common paster adhesive formulation consists of poly(vinyl alcohol)—clay—starch blends (10). A 100% area adhesive coverage is used. The rate of bond strength development of the adhesive is an important commercial concern and rapid bond formation rates are desirable. 

Other typical pyrotechnic fuels include charcoal, sulfur, boron, siUcon, and synthetic polymers such as poly(vinyl alcohol) and poly(vinyl chloride). Extensive use has been made of natural products such as starches and gums, and the use of these materials continues to be substantial in the fireworks industry. MiUtary pyrotechnics have moved away from the use of natural products due to the inherent variabiUty in these materials depending on climatic conditions during the growth of the plants from which the compounds are derived. 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

Commercial starch is mainly com starch, but smaller amounts of sorghum, wheat, and potato starch are also produced. In 1992, 1303 million bushels (45.8 X 10 m ) of com were ground for starch and other products (120) 1 m com weighs - 721 kg and yields 438 kg starch, 26 kg oil, and 142 kg combined gluten and hulls. In the United States in 1994—1995, 462 million bushels were used to produce high fmctose com symp, 231 million bushels went to produce D-glucose, 533 million bushels were used for alcohol production, and 247 million bushels were converted to starch (121). 

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