DE3143082A1 - "CELLULOSE PRODUCT" - Google Patents

Abstract

The product according to the invention which is essentially used as a food additive, is provided as particles which are water-insoluble, yet water-swellable. The inside of those particles is comprised of polysaccharides, bound in 1.4 positions by a beta -glycosidic bond, essentially of cellulose or chitin; the surface of those particles is comprised of water-swellable derivatives of said polysaccharides.

Description

Cellulose product

The invention relates to a cellulose product made from powdered or microcrystalline cellulose and process for its production.

It is known that powdered cellulose can be used to reduce nutritional value and increasing the crude fiber content can be added to foods. she is odorless and tasteless, when consumed as food causes a feeling of satiety and is excreted unchanged by the human organism.

From a nutritional point of view, however, be against the long-term Consumption of larger amounts of microcrystalline or

powdered cellulose raised concerns. These are justified Keep in mind that because of the size of the particles of microcrystalline or powder cellulose a persorption is possible, including the mechanical passage of solid Components in a structurally unchanged form from the Digestive tract understood in the blood and lymphatic system. Hence the use of larger quantities Powdered cellulose and microcrystalline cellulose in nutritionally reduced foods as well as of pharmaceutical preparations are controversial. In the Federal Republic of Germany are all additives of powder cellulose or microcrystalline cellulose to food forbidden. Water-soluble cellulose derivatives such as methyl cellulose and Carboxymethyl cellulose as a thickener and ethyl cellulose as a carrier for Food coloring.

Water-soluble and insoluble again through subsequent crosslinking Cellulose modifications made are used in hygiene articles, diapers, tampons, as Additive for arable soils to improve the moisture content, for the production of Films and as food additives z. B for baked products, sausage skins, diet products and the like are used. However, these modifications have those listed at the outset Advantages of powder cellulose do not appear.

The present invention is based on the object of cellulose products with advantageous properties of cellulose powder or microcrystalline cellulose provide. In particular, a cellulose product should be created that is suitable as a food additive and does not cause persorption.

It has been shown that this problem can be achieved with a cellulose product can dissolve, which comprises water-insoluble particles that are pure inside Cellulose and, in the surface area, from cellulose derivatives that swell in water exist.

The particles preferably contain the following cellulose derivatives in the surface area: R1, where R1 is an alkyl group with 1 to 3 carbon atoms in front of -C atoms, preferably a methyl group, or CHR2-COOH, where R2 is a hydrogen atom or a group with 1 to 20, preferably 2 to 15, carbon atoms, e.g.

B. denotes an alkyl, alkoxy or alkylene group which can be substituted with cycloalkyl or aryl groups, and their salts or NR4-R5, where R3 and R4 form a double bond or each represent a hydrogen atom and R5 denotes an alkyl group with 2 to 6 carbon atoms and can be substituted with NH2 or OH groups.

For food purposes, the cellulose particles preferably indicate Size of at least 180 μm, preferably at least 200 μm. In the subclaims 4 to 11 are processes for the production of the cellulose products according to the invention described.

The cellulose product according to the invention consists of powdery or microcrystalline cellulose that only modifies the particle surface is. It has been shown that only then can persorption be excluded for food purposes is when the particle size is at least 180 μm, preferably at least 200 μm. For other purposes, the size of the particles used is not decisive.

A modification only on the surface of the cellulose particles can be achieved according to the invention if the activation of the cellulose or other Implementation is carried out in suspension.

According to a preferred embodiment of the method according to the invention is used as suspending agent ammonia or a mixture of ammonia with an organic one Solvent used. The mixing ratio of ammonia to the organic solvent is 0.5: 1.5 to 2: 0. The cellulose powder is preferred before suspension dried and then in suspension with metallic sodium or potassium with Sodium hydride activated to form alkali cellulose. The amount of sodium Potassium or sodium hydride is 5 to 15% by weight, preferably 10% by weight, based on on the weight of the cellulose. The alkali cellulose obtained can then be used for Formation of swellable derivatives, e.g. with alkyl halides with 1 to 3 carbon atoms, are preferably reacted with methyl iodide. The reaction will be in suspension carried out and thus a surface modification of the particles is made possible.

Instead of alkyl halides, CC halocarboxylic acids can also be used be carboxymethyl cellulose or

their derivatives of the formula (Cellulose-O-f CHR2-COOS.

In this formula R2 can mean a hydrogen atom or for one Alkyl, alkoxy or alkylene group with 1 to 20, preferably 1 to 15 carbon atoms, stand. The R2 group can optionally also have further substituents such as cycloalkyl or wear aryl. From the sodium and potassium salts formed first, can through Acidify the free acid can be obtained. As i-halocarboxylic acid are preferred Chloracetic acid, GC-bromobutic acid and d-bromohexadecanoic acid are used. These connections are used in an amount equivalent to the substances used for activation.

According to a further embodiment for the production of the invention Cellulose products is used as a suspension medium Water used and the activation is carried out with oxidizing agents. When using sodium periodate a ring opening takes place as an oxidizing agent and aldehyde cellulose is formed. The dialdehyde obtained is then subsequently treated with an amine of the formula (NH2) nR5 implemented, where n is an integer of 1 or 2 and R5 is an alkyl or hydroxyalkyl group with 2 to 6 carbon atoms means. Suitable amines are, for example, diaminoethane or diaminoethanol.

The reaction with amines is also carried out in a suspension medium carried out, which is inert to the reactants, preferably in Dioxane. If liquid amines are used, the dialdehyde can also be present in the amine be suspended yourself. In this production method, the molar ratio is from cellulose to oxidizer 10: 1 and the amines are in equivalent amount added to the oxidizing agent. This is followed by the reaction with amines a reduction, preferably with sodium borohydride.

Both production methods result in water swellable, insoluble Cellulose products, but their particle character has been retained. Through this becomes relatively large particles of more than 200 / µm of sandy and woody taste taken. It is essential that through the choice of the gentle process and the degree of implementation the ultimate degree of crosslinking from the natural crosslinking of the cellulose originates.

The invention is explained in more detail with the aid of the following examples.

Example 1 .

486 g of cellulose powder are dried at 70 ° C. over P205 in a vacuum and dispersed in absolute diethyl ether (1 liter of ether per 160 g of cellulose). The dispersion is then cooled to -450C and ammonia (500 cm3 / 100 g cellulose) is condensed in.

Then 45 g of sodium are added in pieces.

After the blue color has disappeared, 277 g of methyl iodide are added Addition of the solution implemented in absolute diethyl ether.

The reaction time is 20 hours, with 8 hours worked at -400C will. Then the temperature rises slowly to + 100C.

The product obtained is washed with diethyl ether and acetone and sucked off. The product is then taken up in water, adjusted to pH 3, suctioned off and washed with water to pH 5. Finally, acetone is used again washed, filtered off with suction, air-dried and dried over P205 in a vacuum.

Examples 2 to 4 The procedure of Example 1 is repeated, wherein however, instead of methyl iodide, 390 g of 2-bromobutyric acid, sodium salt, 210 g of chloroacetic acid, sodium salt or 697 g of 2-bromohexadecanoic acid sodium salt are added.

Example 5 3300 g of cellulose are suspended in 1.6 l of water and mixed with a solution of 413 g of sodium periodate. After 24 hours at room temperature the product is suctioned off and washed thoroughly with water. Last is with Rinsed acetone and sucked dry and the product dried over P205 at 60C in a vacuum.

Example 6 486 g of aldehyde cellulose are in a mixed solvent suspended from 3 l of dioxane and 120 g of diaminoethane. After approx.

15 g of sodium borohydride are added for 1 hour at 950.degree.

After 12 hours, 50,000 water, based on dioxane, is added.

After a further 3 hours, it is acidic, alkaline for working up with water and washed neutral and rinsed with acetone. The product is vacuumed over P205 dried at 600 g.

Example 7 The procedure of Example 6 is repeated except that this time a solvent mixture of 3 l of dioxane and 122 g of aminoethanol was used will.

Claims (11)

Claims 1. Cellulose product made from powdered or microcrystalline Cellulose, characterized in that it comprises particles insoluble in water the inside of pure cellulose and in the surface area of swellable in water Cellulose derivatives exist. 2. Cellulose product according to claim 1, characterized in that the particles contain the following cellulose derivatives in the surface area: R1> where R1 is an alkyl group with 1 to 3 carbon atoms, preferably a methyl group, or CHR2-COOH, where R2 is a hydrogen atom or a group with 1 to 20, preferably 2 to 15, carbon atoms, for example an alkyl, alkoxy or alkylene group, which can be substituted with cycloalkyl or aryl groups, and their salts or where R3 and R4 form a double bond or each represent a hydrogen atom and R5 denotes an alkyl group with 2 to 6 carbon atoms and can be substituted with NH2 or OH groups. 3. Cellulose product according to claim 1 or 2, characterized in that that for food purposes the particles have a size of at least 180 μm, preferably at least 200 µm. 4. Process for the production of cellulose products according to claims 1 to 3, characterized in that pulverulent or microcrystalline cellulose is activated in the suspension and reacted on the particle surface. 5. The method according to claim 4, characterized in that for food purposes powdered or microcrystalline cellulose with a particle size of at least 180 μm, preferably 200 μm, is used. 6. The method according to claim 4 or 5, characterized in that as Suspension medium ammonia or mixtures of ammonia with organic solvents, which are inert to the reactants are used and the activation is carried out with metallic sodium or potassium or with sodium hydride and that for further reaction alkyl halides with 1 to 3 carbon atoms, preferably methyl iodide, or sodium or potassium salts of d-halocarboxylic acids, the ind-position Alkyl, alkoxy or alkylene group with 1 to 20, preferably 1 to 15 carbon atoms, which may be substituted by cycloalkyl or aryl groups, preferably contain 2-bromoacetic acid, chloroacetic acid, 2-bromohexadecanoic acid can be used. 7. The method according to claim 6, characterized in that the mixing ratio of ammonia to the organic solvent is 0.5: 1.5 to 2: 0 and that the for Activation substances used in an amount of 5 to 15 wt. T, preferably 10 wt .-% 9 based on the weight of the cellulose, and the alkyl halides or d-halocarboxylic acids in an amount equivalent to the substances used for activation can be used. 8. The method according to claim 4s characterized9 that as a suspension medium Water used and activation with oxidizing agents, preferably with sodium periodate, is carried out and that the obtained Aldehydcelluiose dried and with a Amine of the formula (NH2) nR5 is reacted, where n is an integer of 1 or 2 and R5 is an alkyl or hydroxyalkyl group with 2 to 6 carbon atoms, and then the product obtained is preferably reduced with sodium borohydride. 9. The method according to claim 8 »characterized in that the implementation with amines in an inert suspending agent, preferably dioxane will. 10. The method according to claim 8, characterized in that the suspension medium the liquid amine itself is used for the reaction with amines. 11. The method according to any one of claims 8 to 10, characterized in that that the molar ratio of cellulose to oxidizing agent is 10: 1 and the amines be added in an equivalent amount to the oxidizing agent.