JPH0525241B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides aldehyde group-containing starch ethers,
Regarding its manufacturing method and its uses. Polysaccharide compositions are used in many different industrial applications, such as thickeners, adhesives, sizes, and the like. Polysaccharides such as starch and cellulose that have been modified to contain aldehyde groups are particularly used in the paper and textile industry. Both oxidative and non-oxidative methods have been used to introduce aldehyde groups into polysaccharides. The oxidation methods used are periodic acid, periodate salts, alkali metal ferrates or U.S. Pat.
Specification No. 69 (issued to J.Slager on April 23, 1963); Specification No. 3553193 (issued on April 23, 1963);
(issued to D. LeRoy et al. on January 5, 1972); and Specification No. 3632802 (issued on January 4, 1972 to J. LeRoy et al.
Alkali metal bromites such as those described in BeMiller et al.
This includes processing in a similar manner. The non-oxidation process used is described in U.S. Pat.
(published by L. Williams et al.), including reacting polysaccharides with aldehyde-containing agents, such as those described in J.D. Polygalactomannan-gum (i.e., quar gum) and other natural galactose-containing polymers modified with aldehyde groups are useful as crosslinking agents and in the preparation of self-supporting films in various film manufacturing applications. It is used as an adhesive or binding agent. Such aldehyde
Gum derivatives can be prepared by similar oxidative- and non-oxidative methods as described above or in U.S. Pat. No. 3,297,604 (issued January 10, 1967 to F. Germino). Polygalactomanone and other natural polysaccharides with a galactose sequence at _{the C4} position (i.e. , talose). Although commercially available useful polysaccharide aldehydes are obtained by a variety of oxidative and non-oxidative methods, new polysaccharide compositions that also contain aldehyde functionality and have unique flow properties are sought after in a wide range of industries. requested. Therefore, there is a need for aldehyde-containing heteropolysaccharides that can withstand crosslinking reactions alone or with other organic compounds. No such products are disclosed or suggested in any of the above-mentioned documents. The present invention uses R'-O-A-O-starch [wherein A is -CH ₂ CH ₂ - or

[Formula], starch-O is a starch molecule, and R' each has an oxygen atom bonded to a glycoside carbon atom of a monosaccharide by an acetal bond and to the starch by an ether bond. The present invention provides aldehyde group-containing starch ethers (hereinafter sometimes referred to as aldehyde-containing heteropolysaccharides) having a structure in which galactose is located at position ₄ . Representative monosaccharides include hexoses such as glucose, mannose, galactose, talose, gulose, allose, altrose, idose, fructose and sorbose, and pentoses such as xylose, arabinose, ribose and lyxose. Corn and wheat starch ether derivatives in aqueous solution after gelatinization exhibit suitable cooking properties. Such cooking stability allows such derivatives to be used, for example, in various food and thickening applications. Aldehyde-containing starch ether derivatives are prepared by (a) forming a starch base with the structural formula R′-O-A-X (wherein,
A and R' are as above and X is a chlorine or bromine atom) in an aqueous medium with 0.1 to 100% by weight (based on starch) of a glycoside reactant. by reacting for 0.5 to 20 hours at a pH of 13 and a temperature of 20 to 95 °C, and (b) isolating the resulting starch ether, or (a) R″-O-CH ₂ -CH ₂ - O-starch or [where starch -O- is a starch molecule and
R″ is a hexose with a galactose sequence in the C ₄ position with the oxygen attached to the glycoside carbon atom of the hexose by an acetal bond and to the starch by an ether bond, respectively.

[Formula]. ] and (b) a mixture of a galactose-oxidase enzyme in the presence of oxygen. The present invention is also an artificial flavor additive containing the above aldehyde group-containing starch ethers. Glycosides can be made from monosaccharides and polysaccharides containing reducing carbon atoms. This carbon atom located on the terminal sugar ring can react with an alcohol to form a glycoside product, linked by an acetal or ketal linkage, depending on the monosaccharide or saccharide used. A. Halohydrin and Glycidyl Glycoside Reactants One type of glycoside suitable for use as a reactant in making the glycoside starch ethers useful in the present invention includes the formula

[expression] or

[wherein R″ has the above meaning and is a monosaccharide having a galactose sequence in the C ₄ position and an oxygen atom (O) is bonded to the glycoside carbon atom of the monosaccharide, i.e. , C _1- position -- and A and A' are a hydroxyl group or a halogen atom selected from the group consisting of chlorine or bromine.]

It is expressed as Halohydrin or glycidyl glycoside is
It can be made by the method disclosed in US Pat. No. 3,931,148 (issued January 6, 1976 to W. Langdon). In this method,
Glycosides are prepared by reacting monosaccharides with 3-chloro-1,2-propanediol in the presence of about 0.01-2.0% by weight of a strong acid catalyst based on each reactant at a temperature of about 94°C to 108°C. teaches that it can be manufactured. Halohydrin or glycidyl glycoside is
It is advantageously prepared by reacting monosaccharides in excess of 3-halo-1,2-propanediol in the presence of a cationic exchange resin. By using a cationic exchange resin, glycosides can be
At the high temperatures mentioned above, they can be produced at mild temperatures without the carbonization often caused by strong acids of low molecular weight. The reaction is carried out under stirring at a temperature of about 55-80°C for about 3-20 hours. After the reaction is complete, the mixture is
Filter to separate from cationic exchange resin. Excess diol is then removed by vacuum distillation or washing with an organic solvent in order to obtain the 3-halo-2-hydroxypropyl glycoside. Halogenated propanediols that can be used include 3-chloro-1,2-propanediol and 3-bromo-1,2propanediol. It is advantageous to use chlorinated derivatives because they are readily available and inexpensive on the market. Although monosaccharide to diol ratios of less than 1:1.4 have been used, ratios of at least 1:3 to 1:6, especially 1:5 are advantageous. Any cationic exchange resin can be used to produce glycosides. Suitable ion exchange resins include sulfonated cross-linked polystyrenes, such as Rohm and Haas.
Commercially available Amberlite IR-120 from Haas, Dow Chemical
Sulfonated phenols and palmtites such as Dowex 50 from Chemical and Permutit Q from Permutit, and Duolite C-3 from Diamond Schamrock. (Permutit)
There are sulfonated coals such as Zeo Karb H from Co., Ltd. A particularly preferred cationic exchange resin is Doex 50. The amount of resin used in the present invention is about 1 part resin to 2 to 8 parts by weight of sugar, especially 1 part to 4 to 5 parts by weight of sugar. The glycidyl-glycoside used in the present invention is 3-
It can be prepared by reacting halo-2-hydroxypropyl-glycosides with alkali metal hydroxides to form epoxy groups. Typically, the body is mixed with an alkaline aqueous solution during cooling. This mixture is neutralized with acid and then dissolved in alcohol in order to precipitate the metal salts formed. After filtration, alcohol and water are removed from the glycidyl glycoside by vacuum distillation. B Haloethyl Glycoside Reactant Other types of glycosides that are useful reactants in producing the glycoside starch ethers of _the present invention have the formula R-O- _CH2CH2X [wherein R -O is a monosaccharide, where the oxygen atom (O) is attached to a glycoside carbon atom of the monosaccharide, and X is chlorine or bromine. is displayed. Any monosaccharide with a reducible carbon can be reacted with haloethanol in the presence of a strong acid catalyst or cationic exchange resin by a method similar to that described above to obtain a haloethyl glycoside. Typical monosaccharides include, for example, glucose, fructose, sorbose, mannose, galactose, talose, xylose and ribose. Particularly useful haloethyl-glycosides for making starch ethers that are oxidized by treatment with oxygen have the formula R″-O- _CH2CH2X , where R″ _-O and X are as defined above. It is defined as follows. ] Represented by . In some instances, haloethylene glycosides are advantageously used to prepare the starch ethers used in the present invention. This is because impurities present in 3-halo-1,2-propanediol used in the production of haloethylene glycosides (i.e.,
3-dichloro-2-propanol) is very difficult to remove from the glycosides and reacts with starch itself as a crosslinking agent. Halohydrins, glycyl and haloethyl-glycosides can be used, for example, with starch and starch conversion products derived from any plant source, starch ethers and -esters, cellulose and cellulose derivatives and various plant-gums and gum derivatives with etherification reaction conditions. can react under C. Production of hydroxypropyl and ethyl-glycoside starch ether derivatives Applicable starch bases that can be used in producing the glycoside starch ether derivatives of the present invention include corn, potato, sweet potato, wheat, rice, It can be derived from plant sources including sago, tapioca, waxy corn, sorghum, high amylose corn or the like.
Furthermore, conversion products derived from any of the bases mentioned above, such as dextrins produced by acid and/or thermal hydrolysis reactions, produced by treatment with oxidizing agents such as sodium hypochlorite. Also included are oxidized starches, free-flowing or weak-boiled starches made by conversion with oxygen or mild acid hydrolysis, and derived starches such as ethers and esters. This starch base can be a granular starch or a gelled starch, ie a non-granular starch. Methods for producing modified starch bases according to the invention are well known to those skilled in the art and disclosed in the literature. For example, R.L. Whistler, “Methods in Carbohydrate Chemistry”
Carbohydrate Chemistry)” Volume, 1964,
pp. 279-311; RL Whistler et al. “Starch-Chemistry and Technology”
Technology)”, Volume 1967, Nos. 293-450
Page; and R. Davidson and
See N. Sittig, “Water Soluble Resins,” 2nd edition, 1968, Chapter 2. The starch etherification reaction in the present invention is represented by the following reaction formula: R″ ^-O - _{CH 2 CH 2}
R'', A, A' and It should be noted that the etherification reaction proceeds only under alkaline conditions after the halohydrin group is first converted into the epoxide form. However, this is one embodiment of the reaction for producing new starch derivatives from halohydrin glycosides and starch, which can be represented by the following reaction scheme: _{-O -} CH ₂ CH ₂ Although this is not desired, it is believed that the haloethyl group reacts with the starch molecule by a mechanism involving neighboring groups.Those skilled in the art will appreciate that the starch molecule is a polysaccharide composed of many anhydroglyose units. We recognize that each unit has three free hydroxyl groups (except for the non-reducing terminal glucose unit which has four hydroxyl groups) that can react with the glycoside reactant. The number of substituents or degree of substitution (DS) varies with the particular starch, the ratio of reactants to starch, and to some extent the reaction conditions.Furthermore, the relative reactivity of each hydroxyl group in the anhydroglucose unit is unequal. Some appear to react better with the reactants than others, as it is also known that the monosaccharide moiety of the glycoside reactant also contains free hydroxyl groups. In between, the glycoside reactant may also react with other reactant molecules. In such reactions, saccharide units containing a galactose sequence at the _C4 position and unreacted glycidyl or haloethyl groups that can react with starch A sugar-containing molecule will be obtained that still contains .This reaction will result in no cross-linking as there is only one reactive site per molecule. It can be carried out using an aqueous reaction medium, an organic solvent or by a heat-drying reaction technique in which a wet starch cake is impregnated with a glycoside reactant and then subjected to heat-drying.A particularly advantageous method In , the reaction is carried out in an aqueous medium using a starch-based aqueous slurry or dispersion. The glycoside reactant can be added to the reaction mixture in solid form or as an aqueous solution. Advantageous concentrations of the solution are from 20 to 50% by weight, based on the weight of the reaction. In another method, the glycoside reactant solution is brought to the desired PH value prior to addition to the starch base. This is done by adding sufficient alkali. In yet another variation, dry starch is added to the alkaline solution of the glycoside reactant. The amount of glycoside reactant used in the reaction with starch in the present invention will depend on factors such as the base starch used, the glycoside reactant used, the degree of substitution desired in the final product, and, to some extent, the reaction conditions used. Depending, it can generally vary from about 0.1 to 100% by weight based on dry starch. Starch reactions are carried out under alkaline conditions, 11-13 especially
Perform at a pH value of 11.4-12.4. The alkali can be added to the starch slurry or dispersion before or after adding the glycoside reactant. PH
Values are customarily adjusted by adding sodium hydroxide, potassium hydroxide, calcium hydroxide, tetramethyl-ammonium hydroxide, etc. A particularly preferred base is sodium hydroxide. When the reaction is carried out with granular starch, the reaction is often carried out with a salt, e.g.
Preferably it is carried out in the presence of sodium sulphate in an amount of 10 to 40% by weight. The presence of sodium sulfate suppresses starch swelling and results in a product that is well filterable. Sodium sulfate is not used in calcium hydroxide reactions. The reaction mixture is stirred under desired reaction conditions.
The reaction time can vary between 0.5 and 20 hours depending on factors such as the amount of glycoside reactant used, reaction temperature, PH value, scale of reaction and desired degree of substitution. Generally advantageous reaction times are from 6 to 16 hours. The reaction is carried out at a temperature of 20-95°C, in particular 25-45°C. It will be appreciated by those skilled in the art that using granular starch in an aqueous medium using temperatures above about 60°C will result in swelling of the granules and difficulty in filtration or gelation of the starch. If high reaction temperatures are desired, water-miscible aqueous solutions can be used to prevent swelling. After completion of the reaction, the PH value of the reaction mixture is adjusted to a value of 3-7 with any commercially available acid, such as hydrochloric acid, sulfuric acid, acetic acid, etc. Such acids can generally be added as dilute aqueous solutions. Recovery of the derivative can be easily carried out with the particular method used depending on the starch-based form. The granular starch is therefore recovered by filtration, optionally washed with water to remove any residual salts, and dried. The granular starch product can be drum dried, spray dried or gelled and isolated by alcohol precipitation or lyophilized to form a non-granular product (ie, gelatinized). If the starch product is non-granular, it is purified by dialysis to remove residual salts and isolated by alcohol precipitation or freeze-dried or spray-dried. D Production of aldehyde group-containing starch ethers The aldehyde group-containing starch ethers of the present invention can be produced by the above-mentioned reaction formula and (wherein, the glycoside substituent (R'') is a monosaccharide having a galactose sequence at the _C4 position. can be produced according to the invention by oxidation with oxygen of glycoside starch ethers as described in the following: Galactose and talose are exemplified as such monosaccharides:

【formula】

[Formula] Oxidation at the _C6 position of the glycoside substituent is carried out by incubating the starch ether derivative with galactose-oxidase, dispersed in a buffered aqueous solution in an amount determined by the solubility of each component. It is fulfilled by doing. The reaction is carried out in the pH range of 4 to 9, especially 5 to 8, at a temperature of about 10 to 60 DEG C., preferably at room temperature, in the presence of oxygen. Oxidation takes place in the presence of the enzyme catalase, which is capable of reducing hydrogen peroxide (a byproduct of oxidation) to water and oxygen. After incubation, the enzyme is inactivated (ie, inactivated by removing the oxygen source, heating, or lowering the PH). The starch aldehyde is then isolated in known manner or left in solution. Starch is reacted with 2-haloethyl-galactoglycosides and then oxidized with galactose-oxidase to obtain starch derivatives with randomly generated galactose side chains containing aldehyde groups, for example as shown in the following formula: [In the formula, -Glu-Glu-Glu-Glu- is a starch chain. ] The presence of aldehyde functionality in the starch derivatives of the present invention makes the products useful, for example, as paper strengthening additives. This aldehyde functionality makes starch derivatives useful as co-reacting components in the Maillard reaction, the well-known browning and flavor additive forming reactions that occur in foods (this reaction is described in U.S. Pat. No. 3,716,380 (P.J. Hon Potersberge de la Poterle (von
Pottels−berghe de la Potterke) in 1973 2
No. 3,615,600 and No. 3,761,287 (to CHTT Zevennar and K. Jaeggi, issued October 26, 1971 and September 1973, respectively)
1972) and British Patent No. 1285568 (J.L. Godman et al., 1972).
(published on the 16th of May)). A typical process for making artificial flavor additives using the Maillard reaction involves water, sugars, one or more amino acids and optionally other ingredients such as hydrogen sulfide (see GB 1285568), succinic acid. and hydrocarboxylic acids (see U.S. Pat. No. 3,615,600), polyhydric alcohols (U.S. Pat. No. 3,761,287)
(see US Pat. No. 3,716,380) or lower carboxylic acids or fatty acids (see US Pat. No. 3,716,380). Suitable amino acids include glycine, alanine, proline, hydroxyproline, threonine, arginine, glutamic acid, aspartic acid, histidine, lysine, leucine, isoleucine, serine,
There is valine and taurine. Minor amounts of tyrosine, tryptophan, cystine, phenylalanine and methionine may not be objectionable, depending on the flavor additives desired. Di-, tri- or higher peptides or proteins that provide essential amino acids can also be used. Protein hydrolysis products are an advantageous source. The commonly used saccharides also include monosaccharides or di-, tri- or polysaccharides which yield monosaccharides under the conditions of the Maillard reaction. The aldehyde group-containing starch ethers mentioned above are used as exchange materials for some or all of these sugars. Factors that influence the nature and quality of the flavor additives produced include the nature and relative amounts of sugars, amino acids, and other ingredients optionally used, as well as the amount of water, reaction temperature, and reaction time. All parts and percentages in the following examples are by weight and all temperatures are in °C unless otherwise indicated. The carbonyl content of starch aldehydes was determined by “Quantitative Organic Analysis via Functional Groups”.
Functional Groups” Third Edition, by Sindney Siggia (John Wiley & Sons, Inc.)
Wiley & Sons., Inc.), New York, 1949, No.
Measure as described on page 73. Example 1 This example demonstrates the preparation of the starting halohydrins and haloethyl glycosides used in the present invention. a 3-chloro-2-hydroxypropyl-galactoglycoside 80 g (0.44 mol) in a 0.5 round bottom flask equipped with a condenser, mechanical stirrer and heating means
of galactose, 237 g (2.15 mol) of 3-chloro-1,2-propanediol and 20 g of
H ⁺ type cationic exchange resin (Dowex50W−X8)
Add. Heat this mixture to 60-63℃,
Stir at this temperature for 16 hours. The reaction mixture is cooled and then filtered through gauze cloth to remove the resin. The reaction mixture is clear and pale yellow in color.
Unreacted diol is removed by vacuum distillation (2 mmHg) at 80°C. The wet solid product is suspended in acetone, filtered three times to remove residual impurities, and then dried in a vacuum desiccator. b 2-Chloroethyl-galactoglycoside To the same apparatus described under a are added 80 g galactose, 217 g (2.69 mol) 2-chloroethanol and 20 g Dowex 50W-X8. This mixture was stirred at 55 °C for 16 h and 80 °C.
Stir for a further 4 hours at °C. The cationic exchange resin is removed as described above. Next, unreacted 2-chloroethanol was distilled under reduced pressure (0.1 mmHg) to 30 to 35
℃ and then dried in a vacuum desiccator. Example 2 This example demonstrates the preparation of ethyl-galactoglycoside starch ether. Total 100 parts corn starch and 10x 2-chloroethyl-galactoglycosides (untreated)
is added to a solution of 3.0 parts of sodium hydroxide and 30 parts of sodium sulfate in 150 parts of water. This mixture is stirred at 40-45°C for 16 hours. The pH is then lowered to 5.5 by addition of 9.3% strength aqueous hydrochloric acid. Starch derivative A is recovered by filtration, washed three times with distilled water and air dried. For comparison, an aqueous suspension containing 96 parts water and 8 parts of the derivatized starch product or the underivatized base itself is cooked in a boiling water bath for 20 minutes. Leave the gelled preparation overnight at room temperature before experimenting. The base corn-cooked product forms a gel-film. On the other hand, starch derivative cooked products do not gel and are stable. Example 3 This example demonstrates the preparation of ethyl-galactoglycoside ether of cationic free-flowing starch. Corn hydrolyzed to a final water fluidity of 75 -
The starch is first reacted with 2.7% diethylaminoethyl chloride-hydrochloride (US Pat. No. 2,876,217 (issued March 3, 1959 to E. Paschall)). The cationic fluid starch is then reacted analogously to Example 2 with 30% strength 2-chloroethyl-galactoglycoside. Starch derivative B is also recovered by filtration, washing three times with distilled water and air drying. Example 4 Various starch-based hydroxypropyl-galactoglycoside ethers are prepared according to the method described in Example 2. The reaction data are shown in Table 1.

[Table] Shatomo
Rokosi
E cone 74 20
F Tapioca 80 20

Claims (1)

[Claims] 1 R'-O-A-O-starch [wherein A is -CH ₂ CH ₂ - or [formula], starch -O is a starch molecule, and R' is each an acetal It is a monosaccharide having a galactose sequence in the C ₄ position with an oxygen atom connected by a bond to the glycoside carbon atom of the monosaccharide and to the starch by an ether linkage. ] Aldehyde group-containing starch ethers having the following structure. 2. The aldehyde group-containing starch ethers according to claim 1, wherein the monosaccharide is selected from the group consisting of galactose and talose. 3. The starch is selected from the group consisting of corn, waxy maize and tapioca, their conversion products and products derived therefrom, said derived products being derived by an etherification agent or an esterification agent. and starch ethers containing aldehyde groups according to claim 1, wherein the starch aldehyde contains at least 0.25% carbonyl. 4 R'-O-A-O-starch [wherein A is -CH ₂ CH ₂ - or [formula], starch -O is a starch molecule, and R' each represents a monosaccharide by an acetal bond. A monosaccharide having a galactose sequence at the _C4 position with an oxygen atom bonded to the glycoside carbon atom of and bonded to the starch via an ether bond. (a) A starch base having the structural formula R'-O-A-X, where A and R' are as above, and
is a chlorine atom or a bromine atom) at a temperature of 20 to 95 °C at a pH of 11 to 13 in an aqueous medium with 0.1 to 100% by weight of glycoside reactant (based on starch) The above method for producing aldehyde group-containing starch ethers, which comprises reacting for 20 hours, and (b) isolating the obtained starch ether. 5 R'-O-A-O-starch [wherein A is -CH ₂ CH ₂ - or [formula], starch -O is a starch molecule, and R' each represents a monosaccharide by an acetal bond. A monosaccharide having a galactose sequence at the _C4 position with an oxygen atom bonded to the glycoside carbon atom of and bonded to the starch via an ether bond. (a) R″-O-CH ₂ -CH ₂ -O-starch or [where starch -O- is a starch molecule and
R'' is a hexose with a galactose sequence at the C ₄ position, each with an oxygen attached to the glycoside carbon atom of the hexose by an acetal linkage and to the starch via an ether linkage. ] and (b) a mixture of a galactose-oxidase enzyme in the presence of oxygen to oxidize the C ₆ position of the monosaccharide to form a carbonyl group. 6. The method according to claim 5, wherein the reaction is carried out at about 10-60° C. and a pH of about 4-9 in the presence of a catalase enzyme. 7 R' -O-A-O-starch [wherein A is -CH ₂ CH ₂ - or [formula], starch -O is a starch molecule, and R' is each a glycoside of a monosaccharide by an acetal bond. A monosaccharide having a galactose sequence at the _C4 position with an oxygen atom bonded to a carbon atom and bonded to starch by an ether bond Contains starch ethers containing an aldehyde group having the structure Artificial flavor additives.