JPH061801A - Process for cationing nongranular polysaccharide - Google Patents

Abstract

PURPOSE:To provide a cationic polysaccharide which is good in properties by cationing a polysaccharide under specific conditions under which the polysaccharide can be uniformly and efficiently cationized in a substantially dry state by using a cationic agent in the presence of a solvent and a caustic alkali. CONSTITUTION:A mixture of lower alcohol (e.g. methanol) with water is employed as the solvent and a quaternary ammonium compound (e.g. glycidyltrimethylammonium chloride) is employed as the cationizing agent to cationize the title polysaccharide. The amounts of the polysaccharide (e.g. guar gum), water which includes one present in the gum, and lower alcohol are 100 pts.wt. 4-40 pts.wt., and 5-50 pts.wt., respectively. The polysaccharide is first treated with a caustic alkali (1-8 pts.wt.) in the solvent, and is then allowed to react with the quaternary ammonium compound (5-60 pts.wt.) to cationize the polysaccharide under a slightly humid condition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dry cationization method for non-granular polysaccharides. More specifically, the present invention relates to a method for producing a cationized polysaccharide by reacting a non-granular polysaccharide with a quaternary ammonium compound containing a glycidyl group in a slightly wet state. .

Non-granular polysaccharides mean polysaccharides other than starch. Non-granular polysaccharides include those that are not soluble in water, such as cellulose, and those that are soluble in water, such as polygalactomannan. The present invention is effective for any of them, but is particularly effective for non-granular polysaccharides which are soluble in water.

[0003]

2. Description of the Related Art Non-granular polysaccharides which are soluble in water can be used as a thickener, detergent, textile printing agent, sizing agent, etc. by dissolving them in water as they are. However, aqueous solutions of non-granular polysaccharides have the drawback of being unstable. This is because the aqueous solution of the non-granular polysaccharide greatly changes the viscosity due to a change in pH or temperature, or gels when it encounters a polyvalent metal ion.

Therefore, in order to improve the above-mentioned drawbacks, the non-granular polysaccharide was modified to prepare a derivative of the non-granular polysaccharide, which was used. The modification was often carried out by esterifying, etherifying or hydroxyalkylating the non-granular polysaccharide, but also by cationizing.

Several methods are known for cationizing polysaccharides, including not only non-granular polysaccharides but also granular polysaccharides such as starch. The methods are roughly classified into three methods: an organic solvent method, a water medium method and a dry method.
It becomes one. Among them, the organic solvent method is a method in which a large amount of a hydrophilic organic solvent such as a lower alcohol is mainly used as a solvent, and a polysaccharide is dispersed in the slurry to form a slurry, which is cationized with a cationizing agent in a slurry state. is there. Further, the water medium method uses a large amount of water as a solvent and disperses the polysaccharide in water to form a slurry, or dissolves the polysaccharide in water to form a paste solution, and in this state is cationized with a cationizing agent. Is the way to do it. The dry method is a method in which a small amount of water or an organic solvent is used to cationize a polysaccharide in a slightly wet state with a cationizing agent.

The organic solvent method is described in US Pat. No. 4031307.
And the Japanese Patent Publication No. 60-11921. Among them, the above-mentioned U.S. patent specification is a slurry in which a water-soluble non-granular polysaccharide is dispersed in a large amount of a lower alcohol to form a slurry, and a caustic alkali is added to the slurry to alkali-treat the polysaccharide. It describes a method for obtaining a cationized polysaccharide by adding an alkyl halide quaternary ammonium salt as a cationizing agent and reacting it to remove an alkali halide. However, this method has a drawback that it requires a large amount of lower alcohol, therefore a large reaction vessel is required, and a large amount of alkali halide has to be removed, which makes the method complicated to carry out. Was there. Also, Japanese Patent Publication No. 60-11921 discloses a method similar to that described above, in which starch is used as the polysaccharide, a mixed solvent of water and alcohol is used as the solvent, and a cationizing agent is used. However, the only difference is that a quaternary ammonium compound containing a glycidyl group is used, and there is a drawback that a large reaction vessel must be installed in order to use a large amount of solvent.

The water medium method is described in US Pat. No. 2,876,217, JP-B-46-25875, and JP-A-47-196.
No. 1 publication. Of these, US Pat. No. 28
According to the specification of No. 76217, a starch is dispersed in a large amount of an aqueous caustic alkali solution, and an aqueous solution of a quaternary ammonium compound containing a halohydrin group or a glycidyl group is added thereto and reacted to obtain a cationized starch. However, this method requires a large reaction vessel because a large amount of water is used, and the starch dissolves in water to form a viscous solution, which is not easy to stir and is therefore uniform. There is a drawback that it is not easy to obtain cationized starch. The teaching methods of JP-B-46-25875 and JP-A-47-1961 are almost the same as the teaching methods of the above-mentioned U.S. patent specification, and have similar drawbacks.

The dry method is described in JP-A-48-93684 and JP-B-59-41646. Of these, the former is 40-100% by weight as a solvent for starch.
Since it is described that only water of is used, it means that no organic solvent is used, and since it is decided that the starch is alkali-treated in this, the alkali-treatment becomes non-uniform,
Therefore, the product obtained by cationizing it could not be homogeneous. In the latter case, water and alcohol are separately used as a solvent, and alkali and alcohol are first added to the starch to treat the starch with alkali, and then a cationizing agent and water are added to the total amount of water and alcohol. A method for cationizing the amount of starch to 90% by weight or less is described. However, this method is complicated because water and alcohol are added separately, and in addition, since a quaternary ammonium halide compound is used as a cationizing agent, a large amount of alkali halide is produced as a by-product. Therefore, it has a drawback that it takes a lot of trouble to remove the alkali halide.

As described above, all of the conventional polysaccharide cationization methods have drawbacks. In summary, both the organic solvent method and the aqueous medium method have the drawback that they require the use of a large amount of organic solvent or water and thus a large reaction vessel. Although the dry method does not have such a defect, it has a drawback that a homogeneous product cannot be obtained because it is difficult to carry out the reaction uniformly. In addition, when a quaternary ammonium halide compound is used as the cationizing agent, there is a drawback that it takes time to remove the by-product.

[0010]

SUMMARY OF THE INVENTION The present invention is intended to provide a method for cationizing a polysaccharide without the above-mentioned drawbacks. That is, by using a small amount of solvent as in the dry method described above, it is possible to easily cationize the polysaccharide in a slightly damp state, and to easily remove by-products,
The aim is to provide such a method in which a homogeneous cationized polysaccharide is obtained.

[0011]

The present inventor has attempted cationization reaction of polysaccharides using various cationizing agents. As a result, in the case of a granular polysaccharide such as starch, as described in JP-B-60-11921 and JP-B-59-41646, a cationizing agent should be reacted with a good efficiency of 70-80%. However, in the non-granular polysaccharide targeted by the present invention, US Pat.
As described in the specification No. 307, it has been known so far that the cationizing agent can be reacted only with a low efficiency of the order of 50%.

Therefore, the means for efficiently reacting the non-granular polysaccharide with the cationizing agent was further investigated. As a result, it was confirmed that the use of a quaternary ammonium compound containing a glycidyl group as a cationizing agent enables more efficient cationization than the use of other quaternary ammonium compounds. Furthermore, by using a small amount of a mixed solvent of water and a lower alcohol as a solvent and cationizing the non-granular polysaccharide in the mixed solvent only in a state where it is slightly swollen, the reaction vessel can be made smaller. I found it. To that end, with respect to 100 parts by weight of the non-granular polysaccharide, the amount of water including water contained therein is 4-40 parts by weight, and the amount of lower alcohol is 5-50 parts by weight, It has been found that it is necessary to set the amount of caustic to 1-8 parts by weight and the amount of quaternary ammonium compound containing a glycidyl group to 5-60 parts by weight. Among them, especially, when the cationizing agent and the caustic are both dissolved in a mixed solvent of water and a lower alcohol to form a uniform solution, when these materials are mixed to cationize the polysaccharide, It was found that the granulated polysaccharide can be efficiently cationized, and the obtained cationized polysaccharide is uniform and of high quality. The present invention has been completed based on such knowledge.

The present invention is a method for cationizing a non-granular polysaccharide with a cationizing agent in the presence of a solvent and caustic, using a mixed solvent of a lower alcohol and water as the solvent, and cationizing it. Using a quaternary ammonium compound containing a glycidyl group as an agent, the amount of water is 4-40 parts by weight, including the water contained therein, relative to 100 parts by weight of the above-mentioned polysaccharide, and the amount of lower alcohol is 5 to 50 parts by weight, the amount of caustic alkali to 1 to 8 parts by weight, first the non-granular polysaccharide is caustic treated in a mixed solvent, and then 5 to 60 parts by weight of a quaternary glycidyl group-containing quaternary A method for cationizing a non-granular polysaccharide is characterized in that an ammonium compound is added and reacted to cationize the polysaccharide in a slightly wet state. Than it is.

The non-granular polysaccharide that can be used in the present invention is a polysaccharide other than starch, as described above. Among them, those which are insoluble in water, such as cellulose, and those which are soluble in water are included. Further, among water-soluble substances, some are soluble in cold water, and some are insoluble in cold water but are soluble in warm water.

A typical non-granular polysaccharide that is soluble in water is polygalactomannan. Among the polygalactomannans, there are guar gum, locust bean gum, tara gum, cashmere gum and the like. In addition, non-granular polysaccharides include glucomannan such as konjac, tamarind gum, xanthan gum, and silium seed husk. These polysaccharides are preferably used as a fine powder, and are preferably purified and used after removing impurities as much as possible.

In the present invention, caustic is used. Caustic is a quaternary ammonium compound having a non-granular polysaccharide (hereinafter, simply referred to as polysaccharide) and a glycidyl group (hereinafter, referred to as ammonium compound).
When and react, they act as a catalyst. As the caustic alkali, it is suitable to use caustic soda and caustic potash. The amount of caustic is 1-8 parts by weight, preferably 1-6 parts by weight, based on 100 parts by weight of the polysaccharide. The reason for limiting to such a ratio is that if the amount is less than 1 part by weight, the amount of caustic alkali on the surface of the polysaccharide is insufficient and the cationization reaction does not proceed uniformly, and conversely if it is more than 8 parts by weight, This is because the product produced by the cationization reaction is partially gelatinized and a good product cannot be obtained. Also, when the caustic alkali is neutralized with an acid after the reaction is completed, a large amount of salt is produced, which deteriorates the product. Because.

In the present invention, a mixed solvent of water and a lower alcohol is used. Of these, water is
4-40 parts by weight are used for 100 parts by weight of the polysaccharide, including the water content contained in the polysaccharide. Of these, preferred is 10-30 parts by weight. Since water is usually contained in dried polysaccharides in an amount of about several percent, it may not be necessary to add water if wet polysaccharides are used. This water is required for the polysaccharide to react with the caustic to uniformly form an alkali adduct of the polysaccharide. The reason why this amount of water is 4-40 parts by weight is
This is because if the amount is less than 4 parts by weight, the above-mentioned alkali adduct will not be uniformly formed, and if it exceeds 40 parts by weight, the reaction product will be locally gelatinized to form a non-uniform product. is there.

The lower alcohol in the present invention is necessary for keeping the polysaccharide in a wet state, particularly for reducing the water-dissolving power of the polysaccharide and keeping the polysaccharide in a swollen state. To be done. The lower alcohol is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the polysaccharide. Among them, preferred is 10-40 parts by weight. Preferable specific examples of the lower alcohol are methanol, ethanol and propanol. These can be used alone or in combination.

It is desirable that the mixing ratio of water and lower alcohol is the same by weight including the water contained in the polysaccharide, or the lower alcohol is more than water. It is preferred that the lower alcohol be 1-6 parts with respect to parts.

The mixed solvent consisting of water and lower alcohol not only causes the polysaccharide to swell to an appropriate degree, but also dissolves the quaternary ammonium compound containing a glycidyl group and caustic to form a uniform solution. It is desirable to do. When the mixed solvent dissolves the above quaternary ammonium compound and caustic to form a uniform solution, the cationization of the polysaccharide is uniformly carried out to obtain a uniform and transparent cationized polysaccharide. You can However, when the mixed solvent does not dissolve the quaternary ammonium compound and caustic alkali to form a uniform solution, the cationization is unevenly performed, and thus a cationized polysaccharide having low transparency is obtained.

For example, in 100 parts by weight of a mixed solvent consisting of 70% by weight of isopropyl alcohol and 30% by weight of water,
When 1 part by weight of caustic soda is added, the caustic soda does not dissolve uniformly and separates into two layers. However, when 20 parts by weight of methanol is added to this solution, the whole solution becomes one homogeneous solution. Thus, when the polysaccharide is treated with the caustic soda solution having a uniform solution, the polysaccharide is uniformly treated with the caustic soda, and a homogeneous alkali-added polysaccharide is produced there.

In view of the relationship with the mixed solvent of water and lower alcohol, it is preferable to maintain the above-mentioned caustic alkali in the mixed solvent at a concentration as high as possible. But,
When the caustic has a solid phase portion in the mixed solvent at a saturation concentration or higher, the portion may cause a heterogeneous reaction. Therefore, it is preferable to adjust the amount of caustic alkali so that the caustic alkali is below the saturated concentration in the mixed solvent and has a high concentration as close to the saturated concentration as possible.

In the present invention, a cationic agent is used. The cationic agent is a quaternary ammonium compound having a glycidyl group. This cationizing agent has the general formula

[0024]

[Chemical 1]

The cationizing agent for starch, which is known as a cationizing agent for starch. Where R ₁ has ₁ carbon
~ 8 represents a straight chain or branched alkyl group, R ₂ , R ₃ and
R ₄ represents a linear or branched alkyl group or aryl group having 1 to 8 carbon atoms, and X represents halogen. A preferred example of an aryl group is a benzyl group and a preferred example of halogen is chlorine. This cationizing agent is solid at room temperature and has a property of being well dissolved in water and a lower alcohol. The cationizing agent is 5-6 with respect to 100 parts by weight of the polysaccharide.
Used 0 parts by weight. A suitable example of a cationizing agent is glycidyl trimethyl ammonium chloride.

In the present invention, the cationizing agent is used together with the mixed solvent to dissolve the cationizing agent in the mixed solvent. At this time, the cationizing agent preferably forms a uniform solution. Because when the mixed solvent is divided into two layers,
This is because, like the above-mentioned caustic alkali, it becomes difficult for the cationization reaction to proceed uniformly. For example, when glycidyl trimethyl ammonium chloride is used as the cationizing agent, an equal weight mixture of a 75% by weight aqueous solution thereof and isopropanol is divided into two layers at low temperature, but becomes a homogeneous phase at 26 ° C. or higher. Therefore, in this case, if the cationization reaction is performed at 26 ° C. or higher, the cationization can be uniformly progressed. Among them, it is preferable to heat to 40-80 ° C to allow the reaction to proceed. The reason is that if the temperature is lower than 40 ° C, the reaction rate is slow and it takes time to complete the reaction.
This is because if the temperature exceeds ℃, the obtained cationized polysaccharide is colored brown and the quality is deteriorated.

In the present invention, the mixed solvent and caustic alkali are first added to the polysaccharide, and then the cationizing agent is added.
There is no particular limitation on the order of adding the mixed solvent and caustic to the polysaccharide. However, the order of addition is
It is preferred that the caustic is first dissolved in the mixed solvent and the resulting solution is added to the polysaccharide, or that the mixed solvent is added to the polysaccharide first and then the caustic is added later.

In the present invention, the mixed solvent and the caustic alkali are added to the polysaccharide and then this is well stirred. When caustic is added as a solid, the polysaccharide becomes fine powder due to friction between the caustic and the polysaccharide during stirring,
It is dissolved in a mixed solvent to form a solution. The solution thus formed, or the solution added as a solution from the beginning,
It adheres to the polysaccharide particles to form an alkali adduct. At this time, the added mixed solvent is no more than 90 parts by weight with respect to 100 parts by weight of the polysaccharide, so that the whole is only slightly wet. Therefore, stirring is easy.

In the present invention, the cationizing agent is added after reacting the polysaccharide with caustic in the mixed solvent as described above. After that, the stirring is further continued. At that time, in order to allow the reaction to proceed smoothly, it is appropriately heated and maintained at, for example, 40 to 80 ° C. Then, the cationizing agent is dissolved in the mixed solvent and reacts with the alkaline adduct of the polysaccharide to produce a cationized polysaccharide. The product thus obtained contains unreacted residues in addition to the cationized polysaccharide. The unreacted residue is mainly caustic and mixed solvent. Therefore, an acid such as acetic acid is added to the reaction product to neutralize the caustic, and the mixture is dried under reduced pressure to remove the mixed solvent.
Thus, the desired cationized polysaccharide can be obtained.

[0030]

According to the present invention, the amount of water is 4-40 parts by weight and the amount of lower alcohol is 5-50, including the water content in 100 parts by weight of the polysaccharide. Since the mixed solvent is used in an amount of about 1 part by weight, the amount of the solvent used is 90 parts by weight at the most, which is a small amount. Therefore, a large reaction container is not required, and the reaction can be easily carried out in a small container. Further, since a mixed solvent of water and a lower alcohol was used as the solvent, the mixed solvent only swelled the polysaccharide to an appropriate degree, and the small amount of the mixed solvent further facilitates the stirring, thus facilitating the cationization reaction. Can proceed. Furthermore, since a quaternary ammonium compound containing a glycidyl group is used as the cationizing agent, the cationization reaction can be efficiently advanced. Moreover, since the amount of the cationizing agent is 5 to 60 parts by weight and the amount of the caustic alkali is 1 to 8 parts by weight, the cationization reaction can be efficiently and uniformly progressed as a whole, and the cationization reaction is completed. After that, the residue can be easily removed, and a high quality cationized polysaccharide can be easily produced. In this respect, the present invention provides a great advantage.

The advantages of the present invention will be specifically described below with reference to Examples and Comparative Examples. In the following examples and comparative examples, simply “parts” means “parts by weight”. Moreover, the measurement of the water content, pH, ash content, substitution degree, and transparency performed there was according to the following method.

(A) Moisture content: Measured using an infrared moisture meter. (B) pH: A 1% by weight aqueous solution was prepared, and after 10 minutes, measured with a pH meter. (C) Ash content: The absolutely dried sample was put in an electric furnace, heated to 700 ° C. for decomposition, and the weight of the residue was measured. (D) Degree of substitution: It was calculated from the amount of nitrogen measured by the semi-Kjeldahl method of the Food Additives Standards Nitrogen Quantitative Method (2) after thoroughly washing with 70% by weight aqueous methanol solution and drying. As described later in (f), the guar gum contains nitrogen derived from proteins and the like, so the substitution degree shown in Examples and Comparative Examples is 0% from the measured value. The value obtained by subtracting 0.01 was shown. (E) Transparency: A 0.5% by weight aqueous solution is prepared, and after 2 hours have passed, a double cross can be identified using a turbidity fluorometer according to the method specified in JIS K 0101-9. The height of the water layer was measured. (F) Purification of guar gum: The guar gum was suspended in a 30% by weight aqueous methanol solution, stirred for 1 hour, allowed to stand overnight, filtered with suction, and then caustic soda dissolved in a mixed solvent of methanol and water. The filtration residue was dispersed in a 10% by weight solution (the ratio of water to methanol was 1: 1 by weight), the mixture was stirred for 1 hour, neutralized with acetic acid, and the suspension was suction filtered. The filtration residue was washed with a mixed solution of methanol and water (the ratio of water and methanol was 1: 1 by weight), dehydrated twice, and then dried. After drying, it was pulverized to obtain purified guar gum. The N% of the powder obtained by pulverizing the powder and passing through a 100-mesh sieve was 0.1%. Substituting this into the formula for calculating the degree of substitution from the nitrogen content, Becomes

[0033]

Example 1 After adding 1000 g of purified guar gum (water content 6%) to a V-type blender, 40 g of water and 1 of methanol
60 g and 40 g of caustic soda were added separately and then stirred at room temperature for 2 hours. The mixture thus obtained was placed in a hermetically sealed container, and degassed under reduced pressure until the pressure in the container reached 100 mmHg. Then, the valve was opened, and a 75% aqueous solution of glycidyl trimethyl ammonium chloride 4
Inject a mixed solution of 00g and 200g of methanol,
The mixture was heated to 0 ° C. and stirred for 4 hours. Then, the inside of the container was decompressed with a vacuum pump and neutralized with acetic acid. After that, depressurize the inside of the container again with a vacuum pump, remove water and methanol,
Cationized guar gum was obtained.

The cationized guar gum obtained is 100
It passed through all of the mesh sieves and had a pH of 6.8 and was uniformly cationized. The degree of substitution is 0.23
The ash content was 4.1%, the transparency was 11.2 cm, and the reaction efficiency was as high as 68%.

40 g of caustic soda was dissolved in 40 g of water and 160 g of methanol to form a uniform solution, and 400 g of a 75% aqueous solution of glycidyl trimethyl ammonium chloride and 200 g of methanol also formed a uniform solution.

[0036]

COMPARATIVE EXAMPLE 1 This comparative example was carried out in the same manner as in Example 1, except that the ammonium compound containing a glycidyl group was not used as the cationizing agent, but an ammonium compound containing a chloroalkyl group was used instead. In addition, isopropanol was used as the lower alcohol, and the amount of water and the lower alcohol was increased, and the slurry was used.
It was different from Example 1. The details are as follows.

To 1000 g of the purified guar gum (moisture content 6%) used in Example 1, 1500 g of isopropanol was added and well stirred, and 60 g of caustic soda and water 9
00 g of the mixture was added slowly. After stirring for 1 hour as it is, a mixed solution of 624 g of a 50% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride and 100 g of isopropanol was slowly added, the liquid temperature was raised to 70 ° C., and the mixture was stirred at 70 ° C. for 5 hours. .
Then, it was neutralized with acetic acid, filtered and dried to obtain a cationized guar gum.

The cationized guar gum obtained had a pH of 6.7 and was uniformly cationized. The degree of substitution is low at 0.17, the ash content is as high as 7.0%, and the transparency is 6.
It was poor at 6 cm, and the reaction efficiency was as low as 52%. Although a large amount of 900 g of water and 1500 g of isopropanol was used as a solvent, the efficiency was poor.

[0039]

[Example 2] Example 1 was put in an airtight container equipped with a stirrer.
After adding 1000 g of the purified guar gum used in (6% water content), 40 g of methanol, 60 g of isopropanol and 40 g of 50% aqueous caustic soda solution were added separately, and the mixture was stirred at 40 ° C for 2 hours and then depressurized while heating to 60 ° C. Dried. One hour later, after opening the valve and injecting 200 g of methanol and 100 g of isopropanol, 250 g of a 75% aqueous solution of glycidyl trimethyl ammonium chloride
Was added and the mixture was stirred as it was for 4 hours. During this period, the temperature inside the reaction vessel was maintained at 70 ° C. Then, it was neutralized with acetic acid and dried under reduced pressure to obtain a cationized guar gum.

The obtained cationized guar gum had a pH of 6.8 and was uniformly cationized. Its degree of substitution is 0.15, ash content is low at 2.2%, and its transparency is 7.0.
cm was good, and the reaction efficiency was as high as 71%.

[0041]

Example 3 The same purified guar gum (moisture content 6%) 10 used in Example 1 was placed in the same container used in Example 2.
After adding 00 g, a mixed solution of 100 g of methanol and 80 g of a 50% aqueous solution of caustic soda was added, and the mixture was stirred at room temperature for 2 hours.
After stirring for a period of time, degassing was performed under reduced pressure until the pressure in the container reached 100 mmHg. Then, the valve was opened and a 75% aqueous solution of glycidyl trimethyl ammonium chloride 3
Inject a mixed solution of 00g and 200g of methanol,
The temperature was raised to 0 ° C. and the mixture was stirred at this temperature for 3 hours. Then, it was neutralized with acetic acid and dried under reduced pressure to obtain a cationized guar gum.

The obtained cationized guar gum had a pH of 6.6 and was uniformly cationized. The degree of substitution was as high as 0.19, the ash content was as low as 4.1%, the transparency was good at 8.4 cm, and the reaction efficiency was as high as 76%.

[0043]

Example 4 The same purified guar gum (moisture content 6%) 10 used in Example 1 was placed in the same container used in Example 2.
After adding 00g, 40g of 50% aqueous solution of caustic soda
A mixed solution of 160 g of methanol and 60 g of isopropanol was added to the mixture, and the mixture was stirred at room temperature for 3 hours, and then degassed under reduced pressure until the pressure in the container reached 100 mmHg.
Next, the valve was opened, and a mixed solution of 200 g of a 75% aqueous solution of glycidyltrimethylammonium chloride, 100 g of methanol and 100 g of isopropanol was injected, the temperature was raised to 70 ° C., and the mixture was stirred for 4 hours. During this time,
The temperature in the reaction vessel was maintained at 70 ° C. Then, it was neutralized with acetic acid and dried under reduced pressure to obtain a cationized guar gum.

The obtained cationized guar gum had a pH of 6.5 and was uniformly cationized. The degree of substitution is 0.13, the ash content is 2.2%, which is low, and the transparency is 6.9.
cm was good, and the reaction efficiency was as high as 75%.

[0045]

Example 5 The same purified guar gum (moisture content 6%) 10 used in Example 1 was placed in the same container used in Example 2.
After adding 00 g, degassing was performed under reduced pressure until the pressure in the container reached 100 mmHg. Next, 20 g of a 50% aqueous solution of caustic soda, 100 g of methanol, and isopropanol 6
A mixed solution with 0 g was injected, and the mixture was stirred at room temperature for 3 hours. Then, the mixture was degassed under reduced pressure while raising the temperature to 70 ° C. After 1 hour, 7 of glycidyl trimethyl ammonium chloride
A mixed solution of 200 g of a 5% aqueous solution and 100 g of methanol was injected, and the mixture was stirred as it was for 4 hours. During this period, the temperature inside the reaction vessel was maintained at 70 ° C. Then neutralize with acetic acid,
It was dried under reduced pressure to obtain a cationized guar gum.

The obtained cationized guar gum had a pH of 6.6 and was uniformly cationized. The degree of substitution was low at 0.12, but the ash content was low at 1.1%, the transparency was good at 5.7 cm, and the reaction efficiency was high at 70%.

Claims (4)

[Claims] 1. A method of cationizing a non-granular polysaccharide with a cationizing agent in the presence of a solvent and a caustic alkali, wherein a mixed solvent of a lower alcohol and water is used as the solvent and the cationizing agent is used. Using a quaternary ammonium compound containing a glycidyl group, the above-mentioned polysaccharide 100
The amount of water is 4-40 parts by weight, including the water contained therein, and the amount of lower alcohol is 5-5 parts by weight.
0 parts by weight, and the amount of caustic alkali is 1-8 parts by weight. First, non-granular polysaccharide is treated with caustic alkali in a mixed solvent, and then 5-60 parts by weight of quaternary ammonium containing a glycidyl group. A method for cationizing a non-granular polysaccharide, which comprises cationizing the above-mentioned polysaccharide in a slightly moist state by adding a compound and reacting. 2. The method for cationizing a non-granular polysaccharide according to claim 1, wherein the lower alcohol is methanol, ethanol or propanol. 3. The method for cationizing a non-granular polysaccharide according to claim 1 or 2, characterized in that the non-granular polysaccharide is soluble in water. . 4. A quaternary ammonium compound containing a glycidyl group and a caustic alkali are dissolved in a mixed solvent to form a uniform solution.
-3. A method for cationizing a non-granular polysaccharide according to any one of the items 3 to 3.