JPH0651723B2 - Fermentation gum hydroxyalkyl ether and process for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The genus Acetobacter obtained by the present invention.
The hydroxyalkyl ether of fermented gum obtained from Bacter) can be widely used as a thickener, a gelling agent, an excipient, an emulsion stabilizer, and a coagulant.

Acetobacter obtained by the present invention
Fermentation gum hydroxyalkyl ether obtained from (bacter) reduces the change in viscosity of the aqueous solution over time due to bacteria, has a pH of 12 or less and the aqueous solution viscosity is stable, and the aqueous solution has excellent transparency and polyvalent ions. It has the property that it can maintain a high aqueous solution viscosity even in the presence of high concentrations of various salts containing it.

As an application field utilizing this property, as a thickening agent or gelling agent under severe conditions, for example, as a thickening agent or gelling agent in oil well drilling mud composition and oil well hydraulic fracturing composition Available.

(Prior Art) It has been widely known that microorganisms produce polysaccharides. (For example, Atsushiya Harada, Asahi Misaki, "Comprehensive Polysaccharide Science" (below) (December 1, 1974) Kodansha P.)
124-163). Xanthomonas
onas), genus Acetobacter
r), the genus Azotobacterium,
Enterobacter (Aeromonas), Aeromonas (Aeromonas), Bacillus (B)
acillus), Klebsiel (Klebsiel)
la), Erwinia spp., Arthrobacter spp.
Polysaccharides produced by yeasts such as Schizophyllum and Hanseunla (hereinafter referred to as fermentation gum) are thickeners, gelling agents, excipients, emulsion stabilizers, and coagulants. Widely used. These fermented gums contain glucose, sucrose,
Inoculate the strain into an aqueous medium containing carbon sources such as starch degradation products, organic nitrogen such as corn steep liquor, yeast extract and peptone and inorganic nitrogen sources such as ammonium chloride, phosphates, magnesium salts and trace metal salts. The cultivated and produced polysaccharide in the culture solution can be produced through processes such as the culture solution excess and the precipitation of the polysaccharide with alcohol.

These fermented gums are generally cloudy and lack transparency when made into an aqueous solution. Therefore, there are cases in which it is unsuitable for use in fields requiring transparency. Conventionally, in order to increase transparency, for example, as described in Japanese Patent Publication No. 57-5516, a small amount of sodium hypochlorite solution is added to a microorganism culture solution, and after a predetermined time, sodium sulfite or borohydride is added. Although there is a method of adding an appropriate amount of sodium, there is a drawback that the viscosity is lowered. Also,
It was difficult to obtain sufficient transparency. Further, there is a drawback that it is difficult to dissolve in the presence of high concentrations of various salts containing polyvalent ions. In order to improve the solubility, there is a method of esterifying the carboxyl group of xanthan gum as described in, for example, U.S. Pat. No. 3,256,271. For example, a high concentration salt such as a saturated calcium chloride solution is used. It has the drawback that it does not dissolve in aqueous solutions. Also,
With reference to cationized xanthan gum, for example, US Pat. No. 3,505,310 and US Pat.
No. 98,730 and the like have a method of cationizing xanthan gum, but this also has a drawback that it is not dissolved in a high-concentration salt aqueous solution such as a saturated calcium chloride solution.

(Problems to be Solved by the Invention) The present invention has been invented to solve the above problems, and is inexpensive, the aqueous solution is excellent in transparency, and high in various salts containing polyvalent ions. It is an object of the present invention to provide a method for producing a hydroxyalkyl ether of a fermentation gum obtained from Acetobacter, which has the property of maintaining a high aqueous solution viscosity even in the presence of a concentration.

(Means for Solving Problems) As a result of intensive studies to solve the above problems, the present inventors have found that the fermentation gum is hydrophilic in the presence of an alkali metal hydroxide, ammonia, or an organic amine. Aqueous organic solvent and water are used as a medium to react with alkylene oxide, resulting in excellent transparency of the aqueous solution, and under various severe conditions, for example, high aqueous solution even in the presence of high concentration of various salts containing polyvalent ions. It was discovered that the viscosity can be maintained, and the present invention has been completed.

The fermentation gum used in the present invention refers to a heteropolysaccharide of microbial origin, for example, Acetobacter genus (Aceto).
bacterium), Azotobac genus (Azotobac
ter), Enterobacter (Enterobact)
er), Aeromonas (Aeromonas), Bacillus (Kacillus), Klebsiella (Kle)
bsiella), genus Erwinia
a), Arthrobacter
r) and other bacteria, genus Schizophyllum
lum) and other genus of fungi, Hansenula
Examples include polysaccharides produced by yeasts such as a) (hereinafter referred to as fermentation gum).

Examples of polysaccharides belonging to the genus Acetobacter include, for example, Japanese Patent Publication Sho 58
-56640, as described in Acetobacter polysaccharogenes.
polysaccharogenes) MT-11-2
(Microtechnology Research Institute, No. 6174) (FERM P-617
4) etc., K ₂ HPO ₄ 0.1 g, KH ₂ PO ₄ 0.
_{1g, MgSO 4 · 7H 2 O0.25g} , ferric 0.005g chloride, yeast extract 2g and the shoe cloth 30
It can be produced by culturing in a medium containing 1 g of water under aerobic conditions to allow the polysaccharide to accumulate in the culture solution, and after completion of the culturing, precipitation and drying with ethanol.

As a method for reacting a fermented gum with an alkylene oxide, a dry reaction method and a wet reaction method are known. Among them, the wet reaction can be roughly divided into a water medium method and a solvent method, but the method of reacting an alkylene oxide with a fermentation gum in the present invention also uses another water-hydrophilic organic solvent mixed solvent method of the above method. can do.

Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, and mixtures thereof, preferably isopropanol, tertiary butanol, acetone and methyl ethyl ketone.

The weight ratio of the hydrophilic organic solvent as a reaction medium to water is 0: 100 to 100: 0, and particularly 30:70 to 95 :.
A range of 5 is preferred.

When the proportion of water in the reaction medium is less than 5% by weight, the hydroxyalkylation of the fermentation gum and the reaction rate are significantly reduced, and the reaction hardly progresses. Further, the amount of alkylene oxide remaining in the reaction solution after the reaction is extremely large, which is not preferable. As the proportion of water increases, the reaction rate increases, and good reaction conditions can be obtained, and the amount of alkylene oxide remaining in the reaction solution after the reaction also decreases. Furthermore, the effective utilization rate of alkylene oxide is also increased, and a high rate of 80% can be achieved.

When the proportion of water in the reaction medium exceeds 70% by weight, the hydroxyalkyl ether of the produced fermentation gum dissolves in the medium without maintaining the suspension state, and the whole reaction system thickens. For this reason, it becomes impossible to continue the reaction while maintaining the slurry state, but the characteristics of the hydroxyalkyl ether of the fermentation gum of the present invention are not adversely affected.

As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide or the like is used, and as the organic amine, mono,
Di- or trialkylamines such as methylamine,
Ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and the like are used.

The amount of alkali metal hydroxide, ammonia, or organic amine added is based on the anhydro sugar unit of the fermentation gum.
It is 0.04 mol or more. In the course of the hydroxyalkylation reaction of the fermented gum, the role of alkali metal hydroxide, ammonia, or organic amine is a catalyst,
The reaction proceeds even with a small addition amount. However, at an addition amount of 0.04 mol or less of alkali metal hydroxide, ammonia, or organic amine per anhydrosugar unit of the fermentation gum, the resulting aqueous solution of the hydroxyalkyl ether of the fermentation gum is the same as that of the fermentation gum itself. Although it is less cloudy than an aqueous solution, it is still not clear and stable.

Examples of the alkylene oxide include lower alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, butadiene monooxide and glycid. The alkylene oxide may be gaseous or liquid and may be added to the sequential reaction system.

The amount of alkylene oxide used can be arbitrarily changed according to the degree of modification of the fermentation gum, but is 0.02 to 6 mol, particularly 0.1 to 0.1 mol per anhydro sugar unit of the fermentation gum.
-4 mol is preferred.

The reaction is usually carried out between 30 and 100 ° C. The reaction time is a time sufficient to achieve a predetermined denaturing temperature (degree of substitution), and preferably 2 to 24 hours. The form of the reaction vessel is a normal pressure reflux type, a pressure agitator,
A pressure kneader, a pressure blender, or the like may be used. After completion of the reaction, the reaction product can be neutralized, dried and pulverized to obtain a product.

As a side reaction of the reaction of the present invention, the carboxyl group in the fermentation gum is esterified, but it does not adversely affect the transparency and viscosity of the aqueous solution of the hydroxyalkyl ether of the fermentation gum. If necessary, it can be removed by a conventional alkali treatment and used.

Acetobacter obtained
Viscosity of 1% aqueous solution of hydroxyalkyl ether of fermented gum obtained as described above (B-type rotary viscometer, 25 ° C., 60 r
pm, No. 3 spindle) is 5 to 1800 cps, and the degree of substitution is 0.01 to 6, especially 0.1 to 4.

(Function) Since the present invention is constituted as described above, the aqueous solution of the hydroxyalkyl ether of the fermentation gum obtained from Acetobacter is excellent in transparency and under various severe conditions. For example, high aqueous solution viscosity can be maintained even in the presence of high concentrations of various salts containing polyvalent ions.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples. However, the present invention is not limited to the examples. The transparency, viscosity, and degree of substitution shown in Examples, Reference Examples, and Comparative Examples were measured by the following methods.

Measurement of transparency: A sample was added while vigorously stirring distilled water with a homogenizer to prepare a 1% by weight aqueous solution in terms of absolute dry weight of the sample,
This is degassed in a vacuum desiccator and left for 24 hours.
On the other hand, a visible light spectrophotometer model 101 manufactured by Hitachi, Ltd. was remodeled, and a self-made white light transparency measuring instrument in which a concave reflecting mirror was installed in the prism spectroscope was used, and the sample aqueous solution was put into a glass cell with an optical path length of 10 mm The transparency was expressed by the transmittance of distilled water in the same cell as a control, which was expressed in%.

Viscosity measurement: Using the sample aqueous solution after the transparency measurement, the viscosity was measured using a B-type rotary viscometer under the conditions of 25 ° C., 60 rpm, and No. 3 spindle.

Degree of substitution: The sample was treated with alkali to remove the side reaction esterification product, and then dialyzed for 48 hours to precipitate with acetone.
And after drying by the Zeisel-Morgan method;
The degree of substitution was measured.

Reference Example 1 1000 parts of xanthan gum powder having a water content of 13% was added to a pressure-resistant stainless steel closed container of 5 volumes having a stirring blade capable of uniformly stirring the powder, and then sodium hydroxide 2 was added.
A mixed solution of 0 part, 70 parts of water, and 140 parts of methanol was added, and then stirred for 30 minutes. This was sealed and degassed under reduced pressure until the pressure in the container reached 100 mmHg. Then, the valve was opened, 150 parts of propylene oxide was injected, the temperature was raised to 70 ° C., and the mixture was stirred for 10 hours. During this period, the temperature inside the reaction vessel was maintained at 70 ° C. Then, it was cooled, neutralized with acetic acid, dried under reduced pressure for 30 minutes, and pulverized to obtain a product.

The product thus obtained all passed through a 60-mesh sieve, was soluble in cold water, and the aqueous solution was transparent. The sample had a transparency of 68%, a viscosity of 700 cps, and a degree of substitution of 0.36. Further, regarding the stability with time by 1% viscosity in 38% calcium chloride aqueous solution, the viscosity immediately after preparation was 960 cps and after 60 days was 1180 cps, which was stable.

Comparative Example 1 Xanthan gum used as a raw material in Reference Example 1 had a transparency of 25% and a viscosity of 800 cps. Furthermore, regarding the stability with time by 1% viscosity in 38% calcium chloride aqueous solution, the viscosity immediately after preparation was 1260 cps, and precipitation separation occurred after 60 days.

Reference Example 2 1 equipped with a stirrer, a cooler, a dropping funnel and a thermometer
In a 4-necked flask with a capacity of 400 ml of isopropanol,
30 ml of water and 30 g of the xanthan gum powder used in Example 1 having a water content of 13% were charged and stirred to give a uniform suspension dispersion. To this dispersion, a sodium hydroxide aqueous solution prepared by dissolving 3 g of sodium hydroxide in 50 ml of water was gradually added dropwise from a dropping funnel at room temperature, and then stirred at room temperature for 1 hour, and then 35 g of propylene oxide was dropped from the dropping funnel to cover the entire flask. The temperature was raised to 80 ° C. in a hot water bath and the reaction was continued for 7 hours.

After completion of the reaction, the inside of the flask was cooled to 35 ° C. or lower, and acetic acid was gradually added dropwise from the dropping funnel with stirring to neutralize. The reaction system maintained a good suspension state throughout the entire reaction process. Then, the reaction product was filtered, further washed with 200 ml of 80% isopropanol aqueous solution, passed again, further washed with 150 ml of isopropanol, and the reaction product was taken out and dried overnight in a vacuum dryer at 70 ° C. Then, the reaction product was ground with a coffee mill and passed through the entire amount of 80 mesh to obtain a hydroxypropyl ether product of xanthan gum.

This sample had a transparency of 96%, a viscosity of 1000 cps and a degree of substitution of 1.1. Furthermore, regarding the stability over time with a 1% viscosity in a 38% calcium chloride aqueous solution, the viscosity immediately after preparation was 1100 cps, and after 60 days it was 1200 cp.
s, which was extremely stable.

Comparative Example 2 Carboxymethyl hydroxypropyl ether of xanthan gum was produced using the same reaction vessel as in Reference Example 2 and in the same manner according to the following formulation.

Isopropanol 150 ml Water 20 ml Xanthan gum powder 100 g Sodium hydroxide 20 g Water (for dissolving sodium hydroxide) 50 ml Propylene oxide 35 g Sodium monochloroacetate 35 g Water (for dissolving sodium monochloroacetate) 35 ml This sample has a transparency of 91%, a viscosity of 840 cps and hydroxypropoxy. The degree of substitution of the ru group was 0.32, and the degree of substitution of the carboxymethyl group was 0.48. Furthermore, regarding the stability over time due to a 1% viscosity in a 38% aqueous calcium chloride solution, the viscosity immediately after preparation gelled and could not be measured.

Reference Example 3 To a 5-volume stainless pressure-resistant airtight container having a stirring blade capable of uniform stirring, 1000 parts of a xanthan gum culture-finished solution was added, then 5 parts of sodium hydroxide was added, and then 3 parts were added.
Stir for 0 minutes. This is sealed and the pressure in the container is 100
It was degassed under reduced pressure until it reached mmHg. Next, the valve was opened, 80 parts of propylene oxide was injected, the temperature was raised to 70 ° C., and the mixture was stirred for 8 hours. During this period, the temperature inside the reaction vessel was maintained at 70 ° C. Then, it heat-sterilized.

After the reaction and heat sterilization, the inside of the reaction vessel was cooled to 35 ° C. or lower, neutralized with acetic acid, and then the reaction solution was passed through to remove bacterial cells.

The reaction solution was added to 5000 parts of 90% isopropanol to precipitate and dry. The reaction product was crushed and passed through a total of 80 mesh to obtain a product of hydroxypropyl ether of xanthan gum.

The sample had a transparency of 88%, a viscosity of 840 cps, and a degree of substitution of 0.91. Further, regarding the stability with time by 1% viscosity in 38% calcium chloride aqueous solution, the viscosity immediately after preparation was 920 cps and after 60 days was 1160 cps.
And was stable.

Example 1 Xanthan gum was replaced with a polysaccharide of the genus Acetobacter,
The same treatment as in Reference Example 1 was carried out to obtain hydroxypropyl ether, a polysaccharide of the genus Acetobacter.

The product thus obtained all passed through a 60-mesh sieve, was soluble in cold water, and the aqueous solution was transparent. This sample had a transparency of 91%, a viscosity of 800 cps and a hydroxypropyl group substitution degree of 0.26. Furthermore, 38
Regarding stability over time by 1% viscosity in a 1% aqueous calcium chloride solution, the viscosity was 830 cps immediately after preparation and 960 cps after 60 days, which was stable.

Comparative Example 4 The transparency of the Acetobacter polysaccharide used as the raw material in Reference Example 1 was 31%, and the viscosity was 860 cps. Furthermore, regarding the stability over time with a 1% viscosity in a 38% aqueous calcium chloride solution, the viscosity immediately after preparation was 350 cp.
The precipitate was separated after 60 days.

Comparative Example 5 Xanthan gum was replaced with a polysaccharide of the genus Acetobacter,
The same treatment as in Comparative Example 2 was carried out to obtain a hydroxypropyl ether of Acetobacter polysaccharide.

This sample had a transparency of 93%, a viscosity of 820 cps, a hydroxypropyl group substitution of 0.30, and a carboxymethyl group substitution of 0.40. Furthermore, regarding the stability over time due to a 1% viscosity in a 38% calcium chloride aqueous solution, the viscosity immediately after preparation gelled and could not be measured.

(Effect of the invention) As is clear from the above results, the genus Acetobacter (A
The fermented gum hydroxyalkyl ether obtained from (Cetobacter) has excellent transparency of the aqueous solution and maintains a high aqueous solution viscosity under various severe conditions, for example, in the presence of high concentrations of various salts including polyvalent ions. And the effect that can be maintained is very good.

Claims (2)

[Claims] 1. A 1% aqueous solution has a viscosity of 5 to 1800 cps.
(B-type rotational viscometer, 25 ° C., 60 rpm, No. 3 spindle used), and the degree of substitution is 0.01 to 6, preferably 0.1 to 4 (Acetoba genus).
Hydroxyalkyl ether of fermented gum obtained from cter). 2. Fermentation gum is reacted with alkylene oxide, and Acetobacter is characterized.
A process for producing a hydroxyalkyl ether of a fermented gum obtained from (acter).