CS229010B1 - Method of preparing insoluble cellulose derivatives - Google Patents

Description

The invention relates to a process for the production of insoluble spherical cellulose derivatives based on polymer-analogous transformations, in particular the preparation of cellulose ion exchangers, cross-linked cellulose and various functional cellulose polymers.

The spherical highly porous regenerated cellulose prepared according to the author's certificate No. 172 640 (1976) is a new type polymer carrier which can in many cases supplement the known styrene or acrylic-based synthetic carriers. Spherical cellulose finds widespread application in its original form without further treatment, but its particularly important property is its ability to undergo further transformations without disturbing the spherical shape.

Dissociating ionic groups, strongly osmotically acting on the skeleton, can still be introduced into the spherical cellulose, yet the spherical shape remains. All basic ion exchange types with exchange capacities corresponding to the values for commercial non-spherical cellulose ion exchangers were prepared (J. Peska, J. Stamberg, J. Hradil, Angew. Makromol. Chem. 53, 73 (1976)) and in no way did the spherical deformation occur. if the critical conversion limit has not been exceeded. J. Hradil and colleagues also prepared ion-exchange derivatives from spherical cellulose by classical procedures, which are the subject of author's certificate No. 195 205, 199 420 and 188 698.

The chemical reactions leading to the preparation of the basic ion-exchange cellulose derivatives are relatively well known and have been described in monographs (M. Rybák, Z. Bradě, I. M. Hais, Saulenchromatography of Cellulose-Ionenaustauschern, Gustav Fischer Verlag, 1966 ·,

Ε. A. Peterson, Cellulosic Ion Exchangers, North-Holland Publishing Co., 1970) and in original journal literature (EA Peterson, HA Sober, J. Amer. Chem. Soc. 78, 751 (1956), Biochem. Prep. 8, 39 (1961). These are mostly ethereal type reactions

Cel - OH + X - A + NaOH = Cel - O - A + NaX + H ₂ O, wherein X is halogen and A is the remainder of the molecule containing said carboxyl, sulfonic, amine or quaternary exchange group! ammonium. Most of these reactions can also be used for spherical regenerated cellulose prepared according to the author's certificate No. 172 640. However, this new cellulosic material has a considerably different physical structure from the previously used starting forms of cellulose and new problems have emerged in its derivatization.

The spherical cellulose is highly porous since it contains up to 90% by volume of water in the original swollen state, which dilutes the reaction mixture. In order to achieve the reagent concentrations recommended in the known procedures, large excesses thereof are often required. The reaction medium and the reagents need to fill the pores in the cellulosic particles, i.e. 90% of the volume of the particles, and in addition the interparticle space in sufficient quantity to form a stirrable mixture.

This results in a high consumption of chemicals and the derivatization processes become disproportionately expensive. In addition, the presence of the reactants in the interparticle space is generally undesirable since, in the absence of cellulose, side reaction processes take place in the reaction mixture, again increasing the consumption of chemicals and making the preparation more expensive. These complications have been implicated in the introduction of exchange groups, but also in the preparation of cross-linked cellulose in order to obtain lower porosity products and in the preparation of functional celluloses of various types. These disadvantages are overcome by the process for the preparation of the insoluble spherical cellulose derivatives according to the invention.

The essence of the process for the production of insoluble cellulose derivatives by modification of spherical regenerated cellulose by reaction with an alkylating agent in the presence of an alkali metal hydroxide according to the invention is that the reaction is carried out in a heterogeneous medium consisting of an aqueous phase. % than 30 wt. cellulose, wherein the organic phase which is not ground with water and is inert to the reactants is a liquid or a mixture of liquids selected from the group of aliphatic hydrocarbons such as gasoline, aromatic hydrocarbons such as toluene, xylene or its halogenated derivatives such as carbon tetrachloride, monochlorobenzene; in the presence of 0.01-3 Ά wetting agent.

The novelty of the process according to the invention is, in particular, that the course of the chemical reactions is limited to cellulose porous beads, i.e. the intra-particle region, and excreted in the space between the beads, i.e. from the interparticle region. The novel method of carrying out polymer-analogous cellulose conversions, which can be called intra-cellular, brings considerable advantages. Up to now, the known etherification reactions leading to the basic ion-exchange types have been carried out, i.e. to a strongly and weakly acid cation exchanger and a strongly and weakly basic anion exchanger.

However, this does not limit the applicability of the new process, and the same principle can be applied to other reactions. Under similar conditions, it is possible, for example, to crosslink porous cellulose cellulose and to prepare various functional celluloses such as heavy metal sorbets, enzyme immobilization carriers, and the like.

The intra-plate process for carrying out the transformations is achieved by introducing an inert organic liquid into the reaction system. The inert liquid fills the interparticle space and directs the entry of the reactants into the cellulose beads. The inert organic liquid does not mix with water and causes the build-up of reactants in the aqueous medium of the swollen cellulose beads.

The presence of any liquid in the interparticle space is necessary with a view to practicing the reaction, particularly for technological reasons, in order to thoroughly mix the reaction mixture. The use of an inert water-immiscible liquid means a reduction in the need for water-soluble reactants. In a conventional embodiment, an excess of aqueous reagent solution is used to fill the interparticle space, i.e., a solution of caustic and an alkylating reagent in the case of etherification reactions.

In the new embodiment, a lower concentration of alkaline caustic is sufficient and its consumption is close to theory. In addition, the regenerated porous cellulose does not require high concentration (more than 15 Tb) solutions of mercerization for the smooth running of the etherification reaction, even the reverse procedure of adding the reactant components: first the reagent and then the "hydroxide."

The use of an inert water-immiscible liquid to fill the interparticle space directs the reaction to the bead's own mass, limiting the occurrence of an incomplete reaction mixture (without cellulose) in the interparticle space, i.e., in areas where reagents cannot react directly with cellulose macromolecules. This limits the course of side reactions not leading to the desired conversion of cellulose.

For example, in the reaction of chloroacetic acid and sodium hydroxide with cellulose, i.e., in the preparation of a weakly acid cation exchanger derivative by carboxymethylation, hydrolysis of chloroacetic acid to hydroxyacetic acid occurs as a side reaction, thereby reducing conversion to the desired product. In a conventional embodiment, excess reagents have to be used to achieve the required concentration ratios, and said side resection is undisturbed in the interparticle space, since cellulose as the reactant is absent for the main reaction.

The introduction of an inert, water-immiscible liquid into the interparticle space concentrates the reactants in the mass of the beads and the two reaction sequences must compete. In this case, a higher degree of conversion is achieved with less reactants. Other etherification reactions are also accompanied by hydrolytic or other side reactions, so that even in these cases the presence of an inert liquid in the interparticle space can be favored.

The use of an inert water-immiscible liquid will also favorably influence the thermal mode of the modification process. Since the cellulose and the reactants are dispersed as fine particles in an inert dispersion medium, there is no accumulation of reaction heat in the case of exothermic conversions, and in opposite cases, the heat required can be readily supplied via the inert medium. The presence of an inert liquid in the reaction mixture thus facilitates maintaining the required reaction temperature.

The order and manner in which the individual components of the reaction mixture are mixed with one another in the spherical cellulose transformations in the presence of an inert liquid may vary.

For example, the inert liquid is mixed with dry cellulose and an aqueous solution of the reagents is added all at once or sequentially to the suspension. Alternatively, the inert liquid may be mixed with cellulose which has been previously equilibrated with water or with a partial or complete aqueous mixture of the reagents. The reaction may be initiated by supplying one of the reagents or by raising the temperature. Surfactants such as oleic acid, alkyl benzene sulfonates, alkyl naphthalene sulfonates are used to facilitate the conversion of the reagents through the interface and to stabilize the suspension.

According to the invention, various modifications of pearl cellulose can be advantageously carried out, namely 3-sulfo-2-hydroxypropylation using sodium 1-chloro-2-hydroxy-3-propanesulfonate, carboxymethylation with chloroacetic acid, 3-trimethyl-aainoethylation of 3-chloro-2 hydroxypropyltrimethylammonium chloride, 2-diethylaminoethylation with 2-chloroethyldiethylamine hydrochloride, or 3-diethylamino-2-hydroxypropylation with 1-chloro-2-hydroxy-3-diethylaminopropane hydrochloride or 1,1-diethyl-3-hydroxy- azetidinim chloride. .

An important technical effect of the present invention is that the technological performance of the derivatization of spherical porous cellulose is substantially facilitated and that reagent savings are achieved compared to the prior art processes.

All parts and percentages in the examples are parts and percentages by weight.

Example 1

3-sulfo-2-hydroxypropyl cellulose derivative

To 88.5d chlorobenzene was added successively 12.2 d. Of 50% aqueous sodium hydroxide solution, 1.3 d. Of oleic acid and 100 d. Of wet pearl cellulose (water content 85.56) and stirred at room temperature for 1 hour. Sodium solid 1-chloro-2-hydroxy-3-propanesulfonium (27.3 d) was then added and heated to 60 ° C with stirring for 3 hours. The product was separated from the liquid phases, washed with ethanol and water. Capacity: 0.57 mmol -SO4H / g, swelling capacity: 4.9 g water / g.

Sodium 1-chloro-2-hydroxy-3-propanesulfonate

To a solution of 100 d. Sodium pyrosulfite in 119 d. Water heated to 55 ° C was added gradually, in vigorous stirring, 102.8 d. Of 1-chloro-2,3-epoxypropane so that the temperature did not exceed 70 ° C. Ethanol (20) was added and stirred at 70 ° C for 2 hours. The reaction mixture was allowed to cool to room temperature with stirring, the precipitated crystalline product was aspirated, washed with ethanol and air dried: 186.5 d. Concentration of the mother liquor yielded an additional 10.2 d.

Example 2

3-sulfo-2-hydroxypropyl cellulose derivative

To a suspension of 100 d. Dry pearl cellulose (water content 1556) in 550 d. Chlorobenzene and 2.5 oleic acid was added with stirring 165 d. 3056 aqueous sodium hydroxide solution. After stirring at room temperature for 1 hour, a hot solution of 242.5 d. Of 1-chloro-2-hydroxy-3-propanesulfonate in 310 d. Of water was added and the reaction mixture was heated to 60 ° C with stirring for 4 hours. The product was collected, washed with ethanol and water. Capacity: 0.91 mmol -SO4H / g, swelling capacity: 4.5 g water / g.

Example 3

3-sulfo-2-hydroxypropyl cellulose derivative

To 100 d. Wet pearl cellulose (water content 85%) was added 410 d. Acetone and stirred for 1 hour at 40 ° C. Then, the liquid phase is aspirated and the cellulose is added to a suspension of 15 d. Of a 50% aqueous solution of sodium hydroxide in 144 d. Of chlorobenzene and 2 d. Of oleic acid. After stirring at room temperature for 1 hour, the reaction mixture was warmed to 60 ° C and a warm solution of sodium 1-chloro-2-hydroxy-3-propanesulfonene in 44d water was added and stirred at 60 ° C for 3 hours. The product was collected, washed with ethanol and water. Capacity: 0.74 mmol -SO4H / g, swelling capacity:

7.8 g water / g.

Example 4

3-sulfo-2-hydroxypropyl cellulose derivative

To a solution of 1.3 d oleic acid in 74 d. Chlorobenzene was added successively 100 d. Wet pearl cellulose (water content 85%), 0.2 d. Sodium hydroxide, 3. D. Anhydrous sodium sulfate, and the mixture was stirred for 1 hour at Deň: 32 ° C. Sodium hydroxide powder (5.9 d.) Was then added and the mixture was stirred at room temperature for 1 hour. Sodium sulfonate (1-chloro-2-hydroxy-3-propane-5-sulfonate) was added for 3 hours at 60 ° C. After cooling, the product was separated, washed with ethanol and water. Capacity: 0.66 mmol -SO4H / g, swelling capacity: 5.7 g water / g.

Example 5

Carboxymethyl cellulose derivative

To 120 d. White spirit and 2 d. Oleic acid was added with stirring 38 d. 50% aqueous sodium hydroxide solution and then 100 d. Wet crosslinked pearl cellulose (water content 76%). After stirring at room temperature for 1 h, chloroacetic acid (21 d) was added in portions and heated at 70 ° C for 3 h. After cooling, the product was collected, washed with ethanol and water. Capacity: 1.5 mmol -COOH / g, swellability: 4.2 g water / g.

Example 6

3-trimethylamino-2-hydroxypropyl cellulose derivative

To 110 d. Of chlorobenzene, 2 d. Of oleic acid and 1 d. Of 50a, aqueous sodium hydroxide solution was added with stirring 100 d. Of wet pearl cellulose (water content 85%), heated to 60 ° C and added 26.1. D. -chloro-2-hydroxypropyl-trimethylammonium chloride. After 1 h, 10.2 d. Of 50% aqueous sodium hydroxide solution was added and stirred at 60 ° C for 5 h. The product was collected, washed with ethanol and water. Capacity: 1.0 mmol -NCH 3 Cl / g, swelling capacity:

5.6 g water / g.

Example 7

3-trimethylamino-2-hydroxypropyl cellulose derivative

To 85 d. Of chlorobenzene, 1.3 d. Of oleic acid was added 100 d. Of wet pearl cellulose (water content 85%) and then 6.1 d. Of powdered sodium hydroxide and stirred at room temperature for 1 hour. Then 52.2 d. Of a 50% aqueous solution of 3-chloro-2-hydroxypropyl-trimethylammonium chloride was added and stirred at 60 ° C for 5 hours. The product was collected, washed with ethanol and water. Capacity: 1.0 mmol -NfCH3JCl / g, swellability: 5.8 g water / g.

Example 8

2-diethylamino cellulose derivative

To 120 d. Of white spirit and 3.2 d. Of a sulfonate type wetting agent (sodium dodecylbenzenesulfonate) and 100 d. Of wet cross-linked cellulose (water content 76%) were added 38.4 d. Of 2-diethylaminoethyl ethyl chloride and stirred for 1 hour. Deň: 32 ° C. Then, 38 d. 50% aqueous sodium hydroxide solution was added and stirred at 60 ° C for 5 hours. The product was separated, washed with ethanol and water. Capacity: 2.85 mmol -NCgH 4 g / g, swellability: 4.2 g water / g.

Example 9

3 'diethylamino-2-hydroxypropyl cellulose derivative

To 104 d. White spirit, added 100 d. Wet-strength pearl cellulose (water content 76%), 3.2 d. Oleic acid, and 19.4 d. Powdered sodium hydroxide. After stirring at room temperature for 1 h, 1-chloro-2-hydroxy-3-diethylamino-propane hydrochloride (45.2 d) was added and stirred at 90 ° C for 5 h. After cooling, the product was separated, washed with ethanol and water. Capacity: 0.96 mmol ~ N (ϋ ,, Η ^) ,, / g, swellability: 4.0 g water / g.

Preparation of 1-chloro-2-hydroxy-3-diethylaminopropane hydrochloride

A mixture of 50 d. Of diethylamine, 64.4 d. Of 1-chloro-2,3-epoxypropane and 2.1 d. Of water was stirred at 28-30 ° C for 6 hours. The reaction mixture was then neutralized with cooling 161 d. Of 15.5% hydrochloric acid under cooling and then evaporated to the eucha on a rotary evaporator.

When 10 d

3-diethylamino-2-hydroxypropyl cellulose derivative

To 116 d. Of chlorobenzene and 3.2 d. Of oleic acid. Of 19.4 d. Of 50% aqueous sodium hydroxide solution was added 100 d. Of wet cross-linked cellulose (water content 76%). After stirring for 1 h at room temperature, 37.1 d. Of 1,1-diethyl-3-hydroxyazetidinium chloride was added and stirred at 90 ° C for 1 h. After cooling, the product was separated, washed with ethanol and water. Capacity:

0.91 mmol (NH 2 OH) _? / g, swellability: 4.0 g water / g.

Preparation of 1,1-diethyl-3-hydroxy-azetidinium chloride

To 50 d. Of diethylamine and 2.1 d. Of water was added with stirring over 30 minutes 64.3 d. Of 1-chloro-2,3-epoxypropane and maintained at 25-30 ° C for 6 hours. After standing at room temperature for 48 hours, 35 d. Of ether was added with stirring. The separated crystalline product was collected and washed with ether: 94 d.

Claims (1)

A process for the production of insoluble cellulose derivatives by modifying a spherical regenerated cellulose by reaction with an alkylating agent in the presence of an alkali metal hydroxide, characterized in that the reaction is carried out in a heterogeneous environment consisting of an aqueous phase predominantly contained in cellulose particles and organic phases in an amount greater than 30%. wt. cellulose, wherein the organic phase which is not mixed with water and is inert to the reactants is a liquid or a mixture of liquids selected from the group of aliphatic hydrocarbons such as gasolines, aromatic hydrocarbons such as toluene, xylene or their halogenated derivatives such as carbon tetrachloride, monochlorobenzene; in the presence of 0.01 to 3% of a surfactant.