DE1468014C - Process for the preparation of hydroxyalkyl ethers from gactomannans - Google Patents

Description

3 4

The alkylene oxide is added to these suspensions. The reaction according to the invention can be added in gaseous or liquid form. In some cases, it is usually advantageous, open or closed stirred vessels, to carry out the alkylene oxides in a solvent. It can be introduced into the reaction vessel in batches or in a cone solution. be carried out continuously. In the latter case __ As alkylene oxides, for example, question 5 can be used, for example, to pass the reaction mixture through ethylene oxide, propylene oxide, glycide, butene oxide, Bu-temperature-controlled tubes,
tadiene monoxide. At a temperature of about 50 to 60 ⁰ C is

The amount of the alkoxylating agent used, the reaction time about 2 to 4 hours. At higher

if the temperature fluctuates with the desired degree of substitution, the reaction proceeds accordingly

of the conversion product. For making io faster.

ethers that are clearly soluble in cold water are used. from 0.5 to 1, preferably 0.6 to 0.8 parts of alkylene since the resulting hydroxyalkyl ethers of galactooxide to 1 part of anhydrous galactomannan, nannans are insoluble in the reaction medium and so. usually occur in finely divided form. One separates

Suitable catalysts for the process according to the invention, therefore, in a suitable manner by filtering, centrifuging, are primary, secondary and tertiary fuging and pressing off the solvent. With amines and / or quaternary ammonium bases. A large number of aliphatic groups, which can also be interrupted by part of the catalyst and the heteroatoms ent during the reaction, can also be removed from the separated solvents, furthermore cyclo-standing by-products,
contain aliphatic or aromatic groups. In general, it is necessary that the resulting It is also possible that the amino group is constituent crude product by washing out with part of the solution of a heterocyclic ring system. To be cleaned as a catalytic converter. For example, the following are suitable for the batch lyzers: Working preferred embodiment, stirring methylamine, dimethylamine, trimethylamine, tetra- the crude product in a sufficient amount of methylammonium hydroxide, ethylamine, diethylamine, 25 solvents also used in the reaction or triethylamine, tetraethylammonium hydroxide, Isopropylamine, preferably a slightly less watery mixture, pylamine, diisopropylamine, butylamine, dibutylamine, neutralized, filtered or centrifuged and tributylamine, tetrabutylammonium hydroxide, iso-washes with a little solvent. Butylamine, diisobutylamine, the isomeric hexylamine, borrowed, the crude product can also be washed out with a heptyl, octyl, nonyl, decyl and dodecylamine 30 solvent until a neutral reaction occurs, as well as being formed by exhaustive methylation found ammonium bases. Furthermore, but mostly larger than in the case of the above-described aniline, dimethylaniline, cyclohexylamine, piperidine, benen purification processes are mentioned, which include the neutralization of N-methylpiperidine, N-dimethylpiperidineammonibasic constituents. The purified umhydroxyd, pyridine, alkylpyridines, dicyclohexyl- 35 hydroxyalkyl ethers of the galactomannans can be dried anamine, pyrrolidine, benzylamine and dimethylbenzyl- closing.

amine. As representatives of amines, which further The hydroxyalkyl which can be prepared according to the invention

Functional groups contained in the molecule are covered by natural galactomannans in ether

for example called: ethanolamine, diethanolamine, very pure form. The ash content, determined as

Triethanolamine, propanolamine, dipropanolamine, tri-4 ° sulfated ash, is usually below 1% · They are in water

propanolamine. It is also possible to make such amines easily soluble.

to use which has more than one amino group. The products which can be prepared according to the invention can be contained in the molecule, such as. B. Ethylenediamine, use in most cases where propylenediamine, diethylenetriamine, etc. Of the permanent hydrocolloids are desired. The above-mentioned amines or quaternary 45 can be used, for example, as water-soluble ammonium bases, about 0.5 to 20% are required, binders, as thickeners for textiles, in particular 3 to 10%, based on the galacto or other printing inks and as sedimentation, mannan. The required additional amount depends on filtration and flotation aids,
in general according to the basicity and the molecular weight of the catalyst. The speed of the etherification, inter alia, the reaction speed field viscometer at 20 revolutions per minute is dependent on the height of the 5 ° in each case in a 2% aqueous solution with Brook additive. In general, spindle 7 is used to measure
by increasing the amount of amine or the R ^-1 Ii
quaternary ammonium base the reaction rate example
age increased. It should be noted, however, that the 55 57 g of commercially available pure guar flour (Feuchtiger-mentioned catalysts even with alkylene oxydene content 12.3%) were able to react in a solution of. So if you use a lot of them, 5 g of dimethylaniline in 100 g of 70% isopropanol, a corresponding amount of alkylene oxide is dispersed in with vigorous stirring. The secondary reactions obtained are lost and are therefore no longer available for dispersion in a stirred autoclave with 30 g of etherification reaction. 60 propylene oxide added and with constant stirring

The inventive process is heated for 3 hours at 6O ⁰ C in temperature range.

was temperatures of about 30 to 8O ⁰ C, especially 50 to After cooling of the reaction mixture

6O ⁰ C carried out. Below 30 ⁰ C, the reaction of the resulting Hydroxypropyläther is filtered off. The

tion rate for the practical implementation of the crude product was in 100 g of 90% isopropanol

already too low. At higher temperatures, about 65 stirred up and neutralized with acetic acid. To

above 8O ⁰ C, running side reactions in reinforced Filter, was charged with 50 g of isopropanol

Measures from which discoloration of the reaction was washed and the thus purified product in the

Product. Vacuum drying cabinet dried at 70 ^° C.

68 g of a pale yellowish powder were obtained which turned into a clear solution in water solved. The viscosity of the 2% solution was 1100 cP. The ash content (sulfated ash) of the dried Product was 0.7%.

Example 2

57 g of commercially available pure guar flour (moisture content 12.3%) were dispersed in a solution of 3 g of triethylamine in 100 g of 80% acetone by vigorous stirring. The resulting dispersion was placed in an autoclave with 30 g of ethylene oxide and heated for 3 hours at 6O ⁰ C with continuous stirring.

After the reaction mixture had cooled down, the hydroxyethyl ether formed was filtered off, with 100 g 90% strength, then washed twice with 50 g of pure acetone each time and in a vacuum drying cabinet at 70 ° C dried.

72 g of a pale yellowish powder were obtained, the 2% strength aqueous solution of which was clear. It had a viscosity of 1000 cP. The sulfated ash content of the dry product was 0.5%.

Example 3

57 g of commercially available pure guar flour (moisture content 12.3%) were dispersed in a mixture of 80 g of isopropanol and 25 g of a 20% aqueous solution of tetraethylammonium hydroxide. This dispersion was mixed with 30 g of ethylene oxide in an autoclave and heated to 60 ° C. ^{3 ×} / _{2 hours with constant stirring.}

After cooling, the reaction mixture was filtered. The hydroxyethylether was stirred up in 100 g 90% isopropanol ', neutralized with acetic acid to phenolphthalein ", filtered and washed with 50 g of isopropanol washed. The mixture was then dried in Vakuumtrockenschfänk at 7O ⁰ C.

67 g of a pale yellowish powder ίο (sulfated ash content 0.9%) were obtained, which was dissolved in water clearly resolved. A 2% solution had a viscosity of 1150 cP.

Example 4

55 g of locust bean gum (water content 10.1%) were stirred up in a solution of 5 g of monoethanolamine in 150 g of 80% isopropanol. The obtained dispersion was put into an autoclave with 40 g of ethylene oxide and stirred for 3 hours at 6O ⁰ C.

After cooling, the hydroxyethyl ether formed was filtered off. To clean it, it was stirred up in 100 g of 90% strength isopropanol and, after filtering off, washed with 50 g of pure isopropanol. The product purified in this way was then dried at 70 ^° C. in a vacuum drying cabinet. 73 g of an almost colorless powder (sulfated ash content 1.1%) were obtained, the 2% strength aqueous solution of which was clear. It had a viscosity of 950OcP.

Claims (4)

1 to 10 times the amount by weight of an approximately 10 to 50%, claims: in particular 20 to 30 ° / 0 water-containing, water-miscible organic solvent, wel- 1. Process for the preparation of Hydroxyalkyl- ches under the reaction conditions with the alkyl ethers of galactomannans by reacting 5 lenoxide practically does not react, suspended and at of galactomannans with lower alkylene 30 to 80 ⁰ C in the presence of 0.5 to 20% (based oxides in the presence of alkaline agents, d a- on galactomannan) an amine and / or characterized in that the quaternary ammonium base as a catalyst reacts with the galactomannans in about 1.5 to 10 times the alkylene oxide and then the amount by weight of about 10 to 50% water io those hydroxyalkyl ethers of the galactomannans isolated by containing, water-miscible organic filtration or centrifugation.
Solvent, which reacts, suspended and at 30 to 8O ⁰ C lactomannans, such as. B. guar or carob presence of 0.5 to 20% (based on the 15 kernel flour, which are obtained by grinding the endosperm of the galactomannan) of an amine and / or a seed of the guar bean or the carob tree quaternary ammonium base as a catalyst. You can convert both the raw alkylene oxide and then use the products as well as purified flours,
Hydroxyalkyl ethers formed from galacto- To disperse the galactomannans, inannans can be isolated by filtering or centrifuging 20 water-miscible organic solvents. Question which of the selected reaction conditions 2. The method according to claim 1, characterized in practically no or only to a small extent draws that one reacts the process with one with the lower alkylene oxides. It suit Weight ratio of suspending agent to gas secondary alcohols such as isopropanol, secondary lactomannan from 1.5: 1 to 3: 1. 25 butanol, secondary amyl alcohols, further tertiary ones 3. The method according to claim 1 or 2, characterized in alcohols such as tert. Butanol and amyl alcohol, furthermore characterized in that 3 to 10% amine or ketones, such as acetone, methyl ethyl ketone, diethyl ketone. quaternary ammonium bases as a catalyst, other water-miscible ones are also suitable pulled on galactomannan, used. Solvents such as dioxane and dimethylformamide. 4. The method according to claim 1 to 3, characterized in that it is also possible to use mixtures of the above-mentioned that one can use the reaction in Tem- ten solvents. With regard to temperatures between 50 and 6O ⁰ C performs. the later cleaning is preferably such Use solvents that have a relatively low boiling point and are therefore easy to evaporate 35 are. The use of primary alcohols such as methanol, ethanol and n-propanol for dispersing The invention relates to a process for or slurrying the galactomannans per se Production of hydroxyalkyl ethers of course also possible. But there the primary hydroxyl groups occurring galactomannans, such as guar and 40 much faster than the secondary and tertiary Locust bean gum (carubine). of the aforementioned alcohols react, the decrease Hydroxyalkyl ethers of these galactomannans, and yields, based on the alkylene oxide used, although the hydroxyethyl and hydroxypropyl ethers are considerably lower in these cases.
known for a long time. The water content of the used for dispersing So far the galactomannans mentioned in an overdone organic solvent should be about 10 to Shot of dilute aqueous sodium hydroxide solution dissolved or 50%, but in particular 20 to 30%, based on dispersed and the solvent mixture with ethylene oxide or propylene oxide. He judges himself offset. The reaction mixture was primarily based on the properties of the solution * temperature left to stand for a long time until that means and is essential for the quality of the whole Alkylene oxide was implemented. Then 5 ° standing hydroxyalkyl ether of the galactomannans. was neutralized and the highly viscous obtained. If you use too little water or you work Solution evaporated to dryness. The resulting in an anhydrous medium, do not become clear The end of the cake was married. It is also known to obtain soluble galactomannan ether. Will be on To produce hydroxyethyl guar by reacting too much water on the other side, so swell Disodium compound of guar with ethylene chlorine- 55 the resulting hydroxyalkylgalactomannans, inshydrin. especially with high levels of implementation In both processes, the hydroxyls formed fall and thus make working up in considerable alkyl ethers more difficult heavily contaminated, in particular by some extent. Sodium salts. Their removal makes because of the solvents mentioned are in a good water solubility of the Galactomannanhydroxy- ^6o amount used, the stirring or alkyl ethers considerable difficulties for the production. pumpable dispersions is sufficient. In general There has now been a method of making it is a weight ratio of solvent Hydroxyalkyl ethers from galactomannans through to galactomannan from about 1.5: 1 to 3: 1 from conversion of galactomannans with lower alkyls. Of course, you can also do a larger one Lene oxides found in the presence of alkaline agents, 65 dilution, approximately in a ratio of 10: 1 which does not have the disadvantages described. The work; however, one becomes out of economic he-process The invention is characterized in that the dilution ratio is weighed as low as possible one can choose the galactomannans in the approximately 1.5 to rig.