CS197914B1 - Process for preparing sulphoalkylpolysaccharides for the preparation of sizing,dressing and laundry agents - Google Patents

Description

The invention relates to a process for the preparation of sulfoalkylpolysaoharides (water-soluble or dilute alkali) directly from native or delignified plant materials,

Plant materials (wood, kphira, agricultural plants, grasses, etc.) contain a mixture of organic substances in different qualitative and quantitative composition, which include extractives (resins, fats, waxes, etc.), lignin and polysaccharides, cellulose, hemicelluloses, pentosan and hexosan type, pectins, starch and the like. The polysaccharide component of plant materials is predominantly used in the woodworking, food and textile industries as well as related industries. Depending on the type of plant material used and its processing, native material wastes (wood waste, sawdust, flour, krai, straw, corn cob, etc.), lignocellulosic waste (resulting from the hydrolysis of the pentosan component) and effluents are produced.

These wastes find only a very limited and incomplete use, most often in the form of conversion to thermal energy or feed. Wastes are not negligible from the economic point of view because in pulp production, they account for 30 to 50% of the wood raw material.

In recent years, efforts to improve the use of wood (a polysaccharide component) ea have been reflected in the work on the preparation of some cellulose ethers, such as: carboxymethylcellulose (D.F. Durso: Svensk Papperst. 2 (1976) p. 50) and cellulose trimethoxalate (M. Rebek,

B. Jurkowitech: Das Papier 31 (1977) 2, 9 e. 371) Directly from wood and other vegetable mate.

197 914 rials. Previously known processes for the preparation of aulfoalkylpolyaaccharides use mainly conventional materials - pulp, cotton, microcrystalline cellulose and starch, whose preparation is associated with the generation of organic waste (t. Kunlak, J. Shepherd: Cs. Pat. 140 983 (1971)). ), J. Shepherd, £ Kuniak: ββ.AO 168 967 (1975), Ebringer, A., Shepherd J .: ffs AO (PV 1172-78), Graaaie, UK: US Pat. 2,580,352 (1951), Dickey J .

B., Nally J. G., US Pat. 2,442,000 (1974).

The essence of the invention is that natively vegetable materials (sawdust, flour, bark, straw, corn cob, etc.) are used as the starting polysaccharide material for the preparation of sulfoalkyl derivatives, to a different degree delignified materials (semi-cellulose, lime-cellulose) etc. These materials and after alkalinization and depolymerization by air oxygen derivatize in organic solvent environment (isopropyl alcohol, acetone, benzene, toluene, dioxane etc.) by one of the known sulfoalkylating agents (halosulfonates, etionic acids, vinylsulfonic acids, propanesulfone, carbylsulfate) at temperatures up to 65 C.

The reaction product obtained contains fractions of sulfoalkylated polysaccharides of different average polymerization and sub-titration degrees, which together with the distribution of the sub-substituents determine their solubility * and extractability. The extraction can be carried out by a one-time or fractional process using water and dilute alkali. Any residue formed is insoluble high molecular weight moieties of the polysaccharides and a substantial part of the lignin component present. The aqueous extracts are used either in the form of thickened solutions or by some of the known dewatering / drying, lyophilization, water exchange with alcohol and the like. Sulfoalkylpolysaccharides (in the form of a salt or acid) precipitate out of the alkaline extracts and after neutralization with acetic or hydrochloric acid, after washing with 80% ethanol and acetone, to form or work up into aqueous solutions.

The advantage of the proposed method for the preparation of sulfoalkylpolysaccharides is that:

- they are cheaper to prepare because expensive cellulose material (pulp, cotton, microcrystalline cellulose, etc.) is not used,

- uses aa total polysaccharide content of plant materials and various wastes (wood sawdust, flour, chickpea, corn cobs, etc.),

- contributes to a more rational utilization of wood mass,

- suitable parameter! by alkalization and activation of the starting material, water- and alkali-soluble sulfoalkylpolysaccharides can be prepared in almost 100% yields.

Water-soluble proportions of sulfoalkylpolysaccharides isolated from non-delignified materials are slightly colored, limiting their application.

Examples of design

EXAMPLE 1 kg of air-dry beech sawdust (0.3-1.7 mm) and from mixing are gradually introduced into an emulsion of 0.8-1.3 liters of 30-40% sodium hydroxide in 15 / isopropyl alcohol and stirring is continued at temperatures of 25-40. ° C for 1 to 4 hours in an air atmosphere. Then

The mixture was allowed to react and 1.2-1.7 kg of propanesulfone with stirring at 65 ° C for 1 to 3 hours. After neutralization with acetic acid and filtration, the product obtained is washed with 80% ethyl alcohol, acetone and dried at 60 ° C. The product (about 1.2 kg) has a sulfur content of 2.3%. Isolation of sulfoalkyl polysaccharides is accomplished by a single extraction with water, 5% sodium hydroxide or 10% sodium hydroxide at a hydromodule room temperature of 1:10 to 15 for 1/2 to 2 hours. with stirring. The aqueous extract was evaporated to dryness in vacuo. The alkaline extracts are neutralized! acetic acid and precipitated with excess alcohol or acetone (ratio 1: 4 to 5) after filtration, washed from the salts with 80% ethyl alcohol, acetic acid and dried at 60 ° C.

Single extraction

extract yield % (% of sulfur) h ₂ o 29.7 0.15 5% NaOH 54.1 0.13 10% NaOH 56.8 0.13 overall extract 56.8 0.14

Rest: 43.2%, sulfur 2.1% and Klason lignin 71.5% ·

Example 2

Procedure as in Example 1 except that the eco-starting material is used! Acetone was used as the reagent and 1 to 2 kg of sodium .alpha.-chloroethylsulfonate as the reagent. The product obtained (about 1.2 kg) has a sulfur content of 3.16%. After single extractions:

Single extraction

extract yield % SS (% of sulfur) h ₂ o 59.4 0.12 5% NaOH 69.7 0.18 10% NaOH 74.5 0.18 overall extract 74.5 0.18

The rest: 25.5%, sulfur 2.85% and Klason lignin 70.2%,

Example 3

The procedure as in Example 1, with the difference that they are used as starting material!

Chloritsne delignified sawdust count (Klauditz W .: Holzforsch. 11, (1957) p. 110), as a reagent (0.4 to 0.8 kg) of sodium vinyl sulfonate and benzene was used as the organic solvent. The product obtained after evaporation of isopropyl alcohol (approx. 1.4 kg) has a sulfur content of 4.75% ·

187 914

Gradual extraction

extract yield % SS (of% sulfur) h ₂ o 71.2 0.28 5% NaOH 26.6 0.30 overall extract 99.8

Example 4

Procedure as in Example 2 except that ground corn cobs were used as the starting material, and sodium halomethyl sulfonate was used as the sulfoalkylating agent. The product obtained (about 1.3 kg) has a sulfur content of 3.26%.

Single extraction

extract yield % SS (% of sulfur) .h ₂ o 47.5 0.20 5% NaOH 58.6 0.19 10% NaOH 72.1 0.15 Example 5 The procedure as in Example 3, with the difference that as the starting material chlorititanized delignified corn cob (Wise L. E. : Ind. Eng. Chem. (1945) p. 63). The product (approx. 1.4 kg) has sulfur content 4.28%. Gradual extraction extract yield % SS (% of sulfur) h ₂ o 67.3 0.28 5% NaOH 31.0 0.26 overall extract 98.3

OF THE INVENTION

Claims (1)

A process for the preparation of sulfoalkyl polysaccharides for the production of sizing, finishing and washing compositions, characterized in that the native, optionally divignified plant material or lignocellulosic waste is treated with a solution of 30 to 40% sodium hydroxide at 25 to 40 ° C for 1 to 4 hours in and then a sulfoalkylating agent having a carbon number in the alkyl chain of 1 to 3 and preferably sodium β-chloroethyl sulfonate or sodium vinyl sulfonate at a molar ratio of polysaccharide-alkali-sulfoalkylating agent of 1: 2.0 to 3.0: 0.5 to 1 is added. In the organic solvent environment, the preferred isopropane is used 197-14 14 of alcohol, isobutyl alcohol, acetone, benzene, dioxane at temperatures of 40 to 65 ° C for 2 to 4 hours and the reaction mixture is extracted once or successively with water or dilute alkali after evaporation of the organic solvent, the aqueous extract is concentrated and dried in vacuo, the alkaline extract aa is neutralized with acetic acid or hydrochloric acid, precipitated with an excess of methanol or ethanol, acetone in a ratio of 1: 4 to 5, desalted and dried.