SK360089A3 - 0-3-trimethylammonium-2-hydroxypropyl derivative of hemicelluloses of (1r4)-beta-d-xylan-type and preparation method thereof - Google Patents

Abstract

This patent describes the derivatives of hemicellulose closed to the type of (1->4)-beta-D-xylan with the structural units represented by formulas (I) and (II) and/or (II) where R1 and R2, which can be the same or different, mean hydrogen or the group with a general formula (IV), where X means hydroxyl, dihydrogenphosphate, hydrogensulphate, chloride or acetate anion, R3 means the structural unit closed to 4-O-methyl-aplpha- -D-glucoronic acid with a general formula (V), in which Y means hydrogen, sodium or potassium, R4 means the unit closed to alpha-L-arabinofuranose with a formula (VI), while the average degree of polymerisation closed to (1->4)-beta-D-xylan is 20 up to 200. The derivatives of hemicellulose are prepared based on that principle, that in the first stage hemicellulose closed to the type of (1->4)-beta-D-xylan with the structural unit represented by the formula (VII) and (II) and / or (III) are being activated wit 1 up to 25 weight percent water solution of alkaline metal hydroxide at the temperature of 15 up to 25 Celsius degrees, for 30 up to 60 minutes, in the second stage they are undertaken to alkylation with the use of 3-chlorine-2-hydroxypropylmethylammonium chloride, at the temperature of 30 up to 80 Celsius degrees, for 2 up to 6 hours, while the molar ratio closed to hemicellulose : alkaline metal hydroxide is 1: 0,2 up to 3: 0,1 up to 2 a dialysed and dried. The prepared product can be applied as the flocculating agent, when talking about water purification and it also can be used as the auxiliary additive in the production of paper.

Description

Polysaccharides containing quaternary ammonium groups are the papermaking, hitherto known, extremely effective auxiliaries in the preparation of flocculation mixtures and the like. Processes for preparing ammonium derivatives of hernia1 in 1ose mixtures present in the alkaline extracts of the viscose process and pulp production utilized the reaction of a mixture of epichlorohydrin with tertiary amines in an alkaline solution of pat. 3,833,577). The disadvantage of the process is that the alkanolamines or polysaccharides (US reaction takes place at large dilution (up to 100 ml 20 wt.% Sodium hydroxide per 7 g hemicelluloses) at 60 ° C. Polysaccharide degradation occurs under such conditions and the reaction to In this method of preparation, undesirable cross-linking of the hemicelluloses epi-chlorohydrin in an alkaline medium may also occur.

such preparation is because after the end of the mineral acid from the technological point of view, a large amount is also required

SUMMARY OF THE INVENTION

The present invention provides an O-3-trimethylammonium-2-hydroxypropyl (1-> 4) -β-xylan hemicellulose derivative. structural units of formulas Ia and II and / or III

In which

R 1 and R 2, which may be the same or different, represent a hydrogen atom or a group of formula (IV), wherein at least one structural unit of the polymer of formula (I) has R 1 or R 2 as a group of formula (IV)

-CH-CH-N ² I

OH ^CH and ch ₃ X CH in which

X is hydroxyl, hydrogen sulfate, chloride

R 3 represents the structural unit g 1 of the cucuronic formula V d of dibasic phosphate or acetate anion of 4-O-methyl-α-D-

OH in which

Y is hydrogen, sodium or potassium,

R 4 represents the structural unit of α-L-arabinofuranose of formula VI

wherein the average polymerization degree of (1-> 4) -β-D-xylan is 20 to 200. Further, the present invention provides a process for the preparation of a (1-> 4) -β- hemicellulose derivative of the 0-3-trimethylammonium-2-hydroxypropyl derivative. D-xylan with structural units of formulas I and II and / or III, characterized in that in the first step, (1 → 4) -β-D-xylan hemicelluloses with structural units of formulas VII and II and / or III, where structural

(VII) units of formulas II and III are as defined above, wherein the average polymerization degree of the (1 > 4) -β-D-xylan backbone is 20 to 200, activated with 1 to 25 masses. % aqueous alkali metal solution at 15-25 ° C for up to 60 min, wherein the molar ratio of hemicellulose: alkali hydroxide is 1: 0.2-3, in the second step they are alkylated with 3-chloro-2-hydroxypropyltrimethylammonium chloride at a temperature of 30 to 80 ° C for 2 to 6 h wherein the molar ratio of hemicellulose: 3-chloro-2-hydroxypropyltrimethyl ammonium chloride is 1: 0.1 to 2 and then dialyzed and dried. Optionally, an organic acid such as acetic acid or an inorganic acid such as hydrochloric, sulfuric and phosphoric acid is added prior to dialysis.

According to the invention, water-soluble xylan-type polysaccharides having a strongly basic ion-exchange capacity, which can be used over a wide pH range in the acidic and alkaline range, are prepared in a simple manner. Furthermore, it is possible in this way to utilize a new potential polysaccharide raw material which is obtained from sawdust waste, from the waste of one-year agricultural plants (corn cob, sticks, straw, bagasse, etc.) as well as from the viscous waste liquor.

Examples of the realization of the invention

Example 1 g of beech sawdust xylene containing 16% 4-O-methyl-D-gluronic acid and an average degree of polymerization of 120 is mixed with 15 ml of 17.5 wt. % aqueous sodium hydroxide solution and activated with vigorous stirring for 60 minutes at 15 ° C. 15 ml of 50 wt. % aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride alkylating agent and reacting the xylan derivative to react with uranium urea at 60 ° C for 2 h with stirring. The reaction mixture was acidified with 10 wt. % hydrochloric acid, dialyzed and precipitated from the solution with 3 times the volume of ethyl alcohol which was dried. The xylan derivative, the proton acid and the chloride anion in the substituent are obtained. The infrared spectrum contains the following identifying bands: 3435, 2920, 1478, 1388, 1249, 1159, 1044, 983, and 898 cm -1. The 13 C-NMR spectrum contains chemical shifts at 173.5; 102.78; 98.62;

83.60; 82.70; 77.46; 74.87; 73,92; 72.46; 69.31; 66.40;

64.06; 61.03 and 55.31 ppm. The nitrogen content is 0.8 wt. %, which corresponds to the exchanged capacity polymerization degree is 110.

0.57 mmol.g-1 and average

Example 2

The procedure is as in Example 1 except that 10 masses are used to acidify the reaction mixture. % acetic acid.

the sodium atom is 1.03 mmol per gram 0.73 ^- 1

A derivative having uronic acid salt and an acetate anion in the substituent is obtained. Content of Materials. %, corresponding to the exchange capacity and the average polymerization degree is 110.

Example 3

Following the procedure of Example 1, the starting polysaccharide is 85% by weight

4-O-methyl-D-glucuronate 20. A 6 ml ratio is activated except that as hemicellulose from waste% D-xylose, 4.5 wt. % acid and an average polymerization degree of 10 wt. % aqueous solution of hemicellulose hydroxide: alkaline sodium hydroxide (molar metal is 1: 0.2) for 30 minutes, and 3 ml of 50 wt. 0.1) at 80 ° C for 2 hours. The reaction mixture was stirred

Activation is carried out at 25 ° C by% xylan derivative in the hydroxyl anion form without acidification. The sodium salt of uronic acid and the substituent is obtained. The product has a nitrogen content of 0.21 wt. X, corresponding to a exchange capacity of 0.15 mmol.g ^-1 and with an average degree of polymerization of 25. The infrared spectrum comprises the following bands: 3415, 2922, 1456, 1402, 1249, 1163, 1046, 984 and 897 cm -1

Example 4

The procedure as in Example 1 except that xylan isolated from 12 wt corn is used. % Of L-arabinose, and an average polymerization degree of 190, which was activated with 41 ml of 37 wt. % aqueous potassium hydroxide solution (mole ratio of hemicellulose: alkali metal hydroxide is 1: 3) at 15 ° C for 1 h and etherified with 60 mL of 50 wt. % of the alkylating agent 3-chloro-2-hydroxymethylammonium chloride (molar ratio of 1ose: hemicel to alkylating agent 1: 2) at 30 ° C for 6 h. The reaction mixture is acidified with 5 wt. % sulfuric acid. After dialysis, a xylan derivative is obtained in the proton form and with the bisulfate anion in the substituent. The nitrogen content is

1.2 wt%, which corresponds to a exchange capacity of 0.86 mmol.g-1 and the average polymerization degree is 180.

Example 5

The procedure was as in Example 1 except that xylan containing 21 wt% was used. % L-arabinose and 7 wt. For alkylation, 12 ml of the 3-chloro-2-hydroxypropyltrimethylammonium chloride alkylating agent is used at 60 ° C for 4 h for alkylation. The reaction mixture was acidified with 10 wt. % phosphoric acid. The derivative is obtained in proton form with a dihydrogen phosphate anion in the substituent. The nitrogen content is 3.3 wt. %, corresponding to a exchange capacity of 2.36 mmol.g ^-1 and the average polymerization degree is 145. The 13 C-NMR spectrum contains the following signals: 173.10; 109.81; 102.89; 98.76; 85.45; 83.60; 79.41; 77.22;

74.49; 73.91; 69.39; 66.39; 64.02; 62.53; 61.05 and 55.32 ppm.

In the sensual use of telnosf

The invention has uses, in. various industries, for example as an additive in paper production and flocculant for waste water treatment.

Claims (2)

A 0-3-trimethyl ammonium-2-hydroxypropyl hemicellulose derivative of the (1-> 4) -β-D-xylene type with structural units of formulas I and 11 and / or III in which: R1 and R2, which may be the same or different, represent a hydrogen atom or a group of the formula IV, wherein at least one structural unit of polymer I has R1 or R2 a group of the formula IV -CH — CH-N2 | OH ^CH 3 ^CH 3 ^X CH (IV), in which X is a hydroxyl, dihydrogen phosphate, hydrogen sulphate, chloride or acetate anion, R 3 is the structural unit of 4-O-methyl-α-D-glucuronic acid of formula V wherein Y is hydrogen, sodium or potassium, R 4 is the structural unit of α-L-arabinofuranose of formula VI, wherein the average (1-> 4) -fi-D-xylan-type polymerization degree is 20 to 200. 2. A process for the preparation of an O-3-trimethylammonium-2-hydroxypropyl (1- > 4) -β-D-xylan hemicellulose derivative according to claim 1, characterized in that in the first step the hemicellulose type ( 1- (4) -β-D-xylan with structural units of formulas VII and II and / or III, (VII) wherein the structural units of formulas II and III are as defined above, wherein the average backbone polymerization degree (1-> 4) -β-D-xylan is 20 to 200, activated with 1 to 25 masses. % aqueous alkali metal solution at a temperature of about 15 ° C to about 15 ° C 25 ° C for 30 to 60 min, wherein the molar ratio of hemicellulose: hydroxide, alkali metal is 1: 0.2 to 3, in the second step alkylation of 3-chloro-2-hydroxypropyltrimethyl ammonium is carried out i house at temperature 30 to 80 ° C for 2 to 6 hours, then dialyzed and dried, wherein the molar ratio of hemicellulose: 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1: 0.1 to 2, optionally adding an organic acid such as acetic acid or inorganic acid such as hydrochloric, sulfuric and phosphoric acid, are then dialyzed and dried.