JP2009102587A - Method for producing cationized cellulose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing cationized cellulose, in which cellulose can be cationized directly, industrially simply and highly selectively. <P>SOLUTION: The method for producing cationized cellulose comprises a step of reacting low-crystallinity powdery cellulose with the glycidyl trialkyl ammoniun salt shown by formula (1) (wherein R<SP>1-3</SP>are the same or different from one another and each a 1-4C hydrocarbon group; X is a halogen atom) in the presence of a catalyst. The low-crystallinity powdery cellulose has ≤50% crystallinity and an alkali metal hydroxide is used as the catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a cationized cellulose useful as a cationic cellulose derivative.

  Cationic cellulose derivatives are used as ingredients in detergent compositions such as shampoos, rinses, treatments, and conditioners, as well as dispersants, modifiers, flocculants, and the like. This cationic cellulose derivative is represented by cationized hydroxyalkyl cellulose, particularly cationized hydroxyethyl cellulose. As a production method thereof, cellulose is not directly cationized, but cellulose is once converted into an etherification agent such as ethylene oxide. It is common to react with cationizing agent such as glycidyltrialkylammonium chloride after reacting with cellulose ether.

However, this cellulose etherification is a process requiring extremely complicated operations. In this cellulose etherification process, first, cellulose, a large amount of water, and a large excess of alkali metal hydroxide are mixed in a slurry state to form so-called alkali cellulose, which requires a cellulose activation treatment called arserization or mercerization. It becomes.
In addition, the alkali cellulose obtained by the arserification treatment is considered that most hydroxyl groups in the cellulose molecule are alcoholates, and is actually about 3 mol amount per glucose unit in the cellulose molecule. 1 mol or more of alkali is contained. Cellulose ether can be obtained by adding an etherifying agent to the cellulose activated by this arseration, but water of the same weight or more remaining during the arseration also reacts with ethylene oxide as an etherifying agent (hydration) Therefore, a large amount of by-products such as ethylene glycol is generated. Since these react with the cationizing agent to produce further by-products, it is necessary to remove these by-products during subsequent cationization, and a large amount of neutralized salt derived from the alkali used for the arseration. It is also necessary to remove this.
On the other hand, a method in which a cationizing agent is directly reacted with alkali cellulose activated by arsylation is also conceivable. However, since the cationizing agent to be used usually mixes with water very easily, it is more than the same weight remaining after arselation. As a result, the water was preferentially reacted with the cationizing agent. As a result, the cationizing agent was wasted, and it was actually difficult to directly cationize the cellulose.

On the other hand, Patent Document 1 discloses a method in which dimethylacetamide containing lithium chloride is used as a solvent, an amine or a tertiary alcoholate catalyst is added, and a cationizing agent is directly reacted with cellulose without passing through cellulose ether. ing. However, in this method, it is necessary not only to pay attention to the amount of water in the dimethylacetamide solvent, but also because the solubility of cellulose in the solvent is not sufficient, the amount of solvent is extremely large, at least 10 times the weight of cellulose is required. In addition, as an additive, lithium chloride, which is an additive, requires almost the same amount as cellulose, and thus has been an industrially large production method as in the above-described method.
Therefore, development of a method for direct cationization to cellulose which is industrially simple and highly selective has been a very useful and to be overcome problem.

JP-A-60-177002

  An object of the present invention is to provide an efficient method for producing cationized cellulose, which is industrially simple and capable of directly cationizing cellulose with high selectivity.

The present inventors have found that the catalytic reaction with the cationizing agent proceeds efficiently and highly selectively by using powdered cellulose having a reduced crystallinity.
That is, the present invention is a cationization represented by the following general formula (2) in which low crystalline powdery cellulose is reacted with a glycidyl trialkylammonium salt represented by the following general formula (1) in the presence of a catalyst. This is a method for producing cellulose.

(Wherein R ^{1 to} R ³ represent the same or different hydrocarbon groups having 1 to 4 carbon atoms, and X represents a halogen atom.)

(In the formula, R ⁴ represents a hydrogen atom or a cationic group represented by the following general formula (3), and all of R ⁴ are not hydrogen atoms. N represents a number of 100 to 2000.)

(Wherein R ^{1 to} R ³ and X are the same as above).

  According to the present invention, it is possible to provide an efficient method for producing cationized cellulose, which is industrially simple and highly selective for directly cationizing cellulose.

[Preparation of low crystalline powdered cellulose]
In general, cellulose is known for several crystal structures, and is defined as crystallinity from the ratio of the amorphous part and the crystal part present in a part. The “crystallinity” in the present invention is natural. The degree of crystallinity of type I derived from the crystal structure of cellulose is shown, and is defined by the degree of crystallinity represented by the following formula obtained from the powder X-ray crystal diffraction spectrum.
Crystallinity (%) = [(I _22.6 −I _18.5 ) / I _22.6 ] × 100 Formula (1)
[I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5 °). Show
Further, the “low crystallinity” of the low crystalline powdery cellulose in the present invention indicates a state in which the ratio of the amorphous part is large in the crystal structure of the above cellulose, and preferably the crystallization obtained from the above formula (1). The degree is desirably 50% or less.
Since the generally known powdered cellulose has a very small amount of amorphous part, the crystallinity thereof is included in the range of about 60 to 80% according to the calculation formula (1) used in the present invention. This is so-called crystalline cellulose, and its reactivity in cellulose ether synthesis is extremely low.

  The low crystalline powdery cellulose used in the present invention can be prepared very easily from a sheet-like or roll-like pulp having a high cellulose purity obtained as a general-purpose raw material. The method for preparing the low-crystalline powdery cellulose is not particularly limited. For example, JP-A-62-236801, JP-A-2003-64184, JP-A-2004-331918, etc. Mention may be made of the preparation methods described.

Moreover, for example, the method of preparing by processing the chip-like pulp obtained by roughly pulverizing the sheet-like pulp with an extruder and further with a ball mill can also be mentioned.
As the extruder used in this method, a single-screw or twin-screw extruder can be used, and from the viewpoint of applying a strong compressive shear force, a so-called kneading disk portion is provided in any part of the screw. There may be. Although there is no restriction | limiting in particular as a processing method using an extruder, The method of throwing a chip-form pulp into an extruder and processing continuously is preferable.
As the ball mill, a known vibration ball mill, medium stirring mill, rolling ball mill, planetary ball mill, or the like can be used. There is no restriction | limiting in particular in the material of the ball | bowl used as a medium, For example, iron, stainless steel, an alumina, a zirconia etc. are mentioned. The outer diameter of the ball is preferably 0.1 to 100 mm from the viewpoint of efficiently amorphizing the cellulose. In addition to the ball, a medium such as a rod or tube can be used as the medium.
The treatment time of the ball mill is preferably 5 minutes to 72 hours from the viewpoint of reducing the crystallinity. In this treatment, in order to minimize denaturation and deterioration due to generated heat, the treatment is preferably performed at 250 ° C. or less, preferably in the range of 5 to 200 ° C., and further if necessary. , Under an inert gas atmosphere such as nitrogen.
By using the method as described above, it is possible to control the molecular weight, and it is possible to easily prepare powdered cellulose having a high degree of polymerization and low crystallinity, which is generally difficult to obtain. As, it is 100-2000, More preferably, it is 100-1000.

The crystallinity of the low crystalline powdery cellulose used in the present invention is preferably 50% or less as determined from the above formula. If the crystallinity is 50% or less, the cationization reaction proceeds extremely well. In this respect, 40% or less is more preferable, and 30% or less is still more preferable. In particular, in the present invention, it is most preferable to use amorphous cellulose that has been completely amorphized, that is, the degree of crystallinity obtained from the above formula is approximately 0%.
The average particle size of the low crystalline powdered cellulose is not particularly limited as long as it can maintain a good fluidity as a powder, but is preferably 300 μm or less, more preferably 25 to 150 μm, still more preferably 20 to 50 μm.

[Production of cationized cellulose]
In the present invention, a low-crystalline powdery cellulose is reacted with a glycidyl trialkylammonium salt represented by the following general formula (1) in the presence of a catalyst to obtain a cationized cellulose represented by the following general formula (2). Obtainable.

In the general formula (2), R ⁴ represents a hydrogen atom or a cation group represented by the general formula (3), and all of R ⁴ are not hydrogen atoms. N is in the range of 100 to 2000, preferably 100 to 1000.
The degree of substitution per glucose unit in the cellulose molecule in the cationic group represented by the general formula (3) introduced into the low crystalline powder cellulose can be set to a desired degree of substitution, preferably It is 0.01-3, More preferably, it is 0.2-2. In addition, the said substitution degree is measured by the method shown in an Example.

In the present invention, a glycidyl trialkylammonium salt represented by the general formula (1) is used as a cationizing agent.
In the general formula (1), R ^{1 to} R ³ represent the same or different hydrocarbon groups having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n- A butyl group, an isobutyl group, a tert-butyl group, etc. are mentioned, Among these, a methyl group is preferable. X represents a halogen atom, and examples include a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
The glycidyl trialkylammonium salt represented by the general formula (1) is obtained by reacting an epihalohydrin such as epichlorohydrin or epibromohydrin with a tertiary amine such as trimethylamine, triethylamine, tripropylamine or tributylamine. Although obtained, the most commonly used is a combination of epichlorohydrin and trimethylamine. Therefore, the combination of R ^{1 to} R ³ and X is preferably a methyl group and a chlorine atom.

When carrying out the present invention, the cationizing agent is dehydrated during the reaction or before the reaction, if necessary, from the viewpoint of maintaining the fluidity of cellulose and reacting in the powder state, and in the reaction system described later. It is preferable to adjust the water content with respect to cellulose.
The amount of cationizing agent used is almost the same as the stoichiometric amount required to introduce a cation group into cellulose with a desired degree of substitution because the reaction efficiency of the cationizing agent with respect to cellulose is extremely high. Can be used. That is, the use amount of the cationizing agent is preferably 0.01 to 3 mol times per glucose unit in the cellulose molecule, and is 0.2 to 0.2 from the viewpoint of performance as a cationized cellulose and dehydration efficiency after the reaction. More preferably, it is 2 mole times.

  Although there is no restriction | limiting in particular as a catalyst used by this invention, A base or an acid catalyst can be used. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, trimethylamine, triethylamine, and triethylenediamine. Secondary amines. Examples of the acid catalyst include Lewis acid catalysts such as lanthanide triflate. Of these, basic catalysts are preferred, alkali metal hydroxides are particularly preferred, and sodium hydroxide and potassium hydroxide are most preferred. These catalysts can also be used 1 type or in combination of 2 or more types.

The catalyst can be added by adding an aqueous solution or dilute solution to remove the excess water, and then reacting. However, the reaction state should be in a slurry state or in a high viscosity state. Therefore, it is preferable to maintain a fluid powder state, and therefore, the water content when added in a dilute aqueous solution is preferably 100% by weight or less based on cellulose.
As the amount of the catalyst used, a catalytic amount is sufficient for both cellulose and the cationizing agent. Specifically, an amount corresponding to 0.1 to 50 mol% per glucose unit in the cellulose molecule is preferable. Further, an amount corresponding to 1 to 30 mol% is more preferable, and an amount corresponding to 5 to 25 mol% is most preferable.
The cationizing agent used in the present invention usually contains a small amount of a halohydrin due to its industrial production method. For example, in the case of glycidyltrimethylammonium chloride, 1-chloro-2-hydroxypropyltrimethylammonium chloride is 1 About 2% may be included. The low crystalline or amorphous cellulose used in the present invention can cause the reaction with these halohydrins by alkali to proceed with a complete stoichiometric reaction, but the alkali is reactive by the stoichiometric reaction. In order to make the reaction with a cationizing agent such as glycidyltrimethylammonium chloride proceed satisfactorily, the alkali requires at least a larger amount of catalyst than is consumed by this halohydrin form.

The reaction between the cellulose and the cationizing agent in the present invention is preferably performed while maintaining the powder state as described above, but can also be performed in a dispersed state using a non-aqueous solvent other than water.
Examples of the non-aqueous solvent include secondary or tertiary lower alcohols such as isopropanol and tert-butanol which are generally used in the arsylation treatment; diglyme such as 1,4-dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. And ether solvents such as triglyme; and hydrophilic solvents such as dimethyl sulfoxide. Among them, dimethyl sulfoxide and isopropanol are preferable, but dimethyl sulfoxide is particularly preferable in order to avoid the possibility that the solvent itself reacts.
The amount of these nonaqueous solvents used is preferably 10 times by weight or less with respect to cellulose from the viewpoint of avoiding a decrease in reactivity due to dilution of the catalyst.

The method for adding a cationizing agent in the present invention is not particularly limited. For example, (a) a method in which a catalyst is first added to cellulose and then a cationizing agent is added dropwise, and (b) a cationizing agent is added to cellulose. The method of adding a catalyst later and making it react is mentioned.
In any method, the water content with respect to cellulose in the reaction system is preferably 100% by weight or less. If the moisture content with respect to cellulose is within this range, the cellulose can be reacted in a fluid powder state without excessive aggregation. In this respect, 80% by weight or less is more preferable, and 5 to 50% by weight is most preferable.
For this reason, in the method (a), it is possible to simultaneously perform dehydration while dropping the cationizing agent and adjust the water content in the reaction system to the above-described range. In the method (b), a cationizing agent is added to cellulose in a lump and dehydration is performed under reduced pressure to adjust the water content to the cellulose within the above-mentioned range, and then the reaction is performed by adding a catalyst and heating. Is possible.

In the present invention, since the reaction selectivity of the cationizing agent to cellulose is high, the by-product of the hydrate (diol body) of the cationizing agent represented by the following general formula (4), which is a main byproduct, is reduced. Can be made.

(Wherein R ^{1 to} R ³ represent the same or different hydrocarbon groups having 1 to 4 carbon atoms, and X represents a halogen atom.)
Therefore, in the present invention, not only can cationization be performed with a desired degree of substitution, but also cationization with a high degree of substitution, which has been extremely difficult in the past, specifically, glucose in cellulose molecules. Cationization with a degree of substitution of 1 or more per unit is also possible.
Further, in the conventional cationization reaction, the base such as alkali used in the reaction is removed as a neutralized salt after the reaction is completed, but since the present invention is a catalytic reaction, the amount of the neutralized salt can also be reduced. Is possible. In other words, since there are very few by-products and wastes derived from the cationizing agent and the catalyst, purification after completion of the reaction (such as washing) is facilitated, and industrial utility is extremely high.

In the present invention, it is preferable to react a mixture of low crystalline powdered cellulose, a catalyst and a cationizing agent in a flowable powder state. However, the cellulose powder and the catalyst or the cationizing agent are previously mixed with a mixer such as a mixer. It is also possible to carry out the reaction after uniformly mixing and dispersing as necessary with a shaker.
Moreover, as a reaction apparatus that can be used in the present invention, one that can mix a low-crystalline powdery cellulose, a catalyst, and a cationizing agent as uniformly as possible is preferable. In addition to a mixer such as the mixer described above, JP 2002-114801 A A mixer such as a so-called kneader, which is used for kneading resins or the like as disclosed in paragraph [0016] of the specification of the Japanese Patent Publication, is most preferable.
As reaction temperature in this invention, the range of 0-100 degreeC is preferable, However, The range of 10-90 degreeC is more preferable, The range of 20-80 degreeC is especially preferable.
Moreover, although this invention is performed under a normal pressure or pressure reduction, when performing under pressure reduction, the range of 1-100 kPa is preferable, and the range of 2-20 kPa is more preferable. Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen, as needed from a viewpoint of avoiding the coloring at the time of reaction.
After completion of the reaction, the catalyst is neutralized with an acid or alkali, washed with water-containing isopropanol, water-containing acetone solvent, etc., if necessary, and then dried to obtain the compound represented by the general formula (2). Cationized cellulose can be obtained.

  In the present invention, the cationic group represented by the general formula (3) may be bonded to the hydroxyl group at any position in the glucose unit in the cellulose molecule, but it can be adjusted to a desired degree of substitution. From this, the cationized cellulose obtained in the present invention can be used for compounding components of detergent compositions such as shampoos, rinses, treatments, and conditioners, and for applications such as dispersants, modifiers, and flocculants. .

(1) Moisture content with respect to cellulose The moisture content with respect to cellulose was measured at 150 ° C. using “FD-610” manufactured by Kett Scientific Laboratory as an infrared moisture meter.
In order to confirm the optimal moisture content of cellulose in the present invention, after adding a predetermined amount of water to the non-crystallized cellulose obtained in Production Example 1 described later, it is vigorously stirred and shaken, and its agglomerated state is visually observed. Were observed repeatedly.
As a result, in order to react cellulose in a fluid powder state, it was determined that the water content was preferably 100% by weight or less. The results are shown in Table 1.

(2) Calculation of crystallinity The crystallinity of cellulose is calculated according to the above formula from the peak intensity of the diffraction spectrum measured under the following conditions using “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation. It was.
X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: 2θ = 5-45 °, measurement sample: produced by compressing pellets of area 320 mm ² × thickness 1 mm, X-ray Scan speed: 10 ° / min
(3) Measurement of degree of polymerization of powdered cellulose The degree of polymerization of powdered cellulose was measured by the copper ammonia method described in ISO-4312 method.
(4) Calculation of degree of substitution The degree of substitution indicates the average amount of cationic groups introduced per unit of glucose in cellulose, and was calculated by a conventional method (colloid titration method) using a polyanion reagent for colloid titration. For the measurement, an automatic titrator AT-150 manufactured by Kyoto Electronics Co., Ltd. was used. Moreover, the confirmation from the measured value of the chlorine content and the nitrogen content by elemental analysis was also performed.
(5) Measurement of average particle diameter of powdered cellulose The average particle diameter of powdered cellulose was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” manufactured by Horiba, Ltd.

Production Example 1 (Production of Amorphized Powdered Cellulose)
A wood pulp sheet (Bolleguard's pulp sheet, crystallinity 74%) was shredded (manufactured by Meiko Shokai Co., Ltd., “MSX2000-IVP440F”) into a chip shape.
Next, the obtained chip-like pulp was charged into a twin screw extruder (“EA-20” manufactured by Suehiro EPM Co., Ltd.) at 2 kg / hr, a shear rate of 660 sec ⁻¹ , a screw rotation speed of 300 rpm, and cooling water from the outside. The powder was processed by one pass while flowing.
Next, the obtained powdered cellulose was put into a batch-type medium stirring mill (“Sand grinder” manufactured by Igarashi Machine Co., Ltd .: container volume 800 mL, filled with 720 g of 5 mmφ zirconia beads, filling rate 25%, stirring blade diameter 70 mm). While passing cooling water through the container jacket, the mixture is pulverized for 2.5 hours at a stirring speed of 2000 rpm and a temperature of 30 to 70 ° C., and powdered cellulose (crystallinity 0%, polymerization degree 600, average particle size 40 μm) Got. For the reaction of the powdered cellulose, an unsieved product (90% of the input amount) with a sieve having an opening of 32 μm was used.
In addition, powdered cellulose with different crystallinity was prepared by changing the treatment time in the ball mill treatment.

Example 1
A 1 L kneader (manufactured by Irie Shokai Co., Ltd., PNV-1 type) was charged with 100 g of the amorphous cellulose (crystallinity 0%, polymerization degree 600) obtained in Production Example 1, and 5% 48% sodium hydroxide aqueous solution 5 g And stirred for 3 hours under a nitrogen atmosphere. Thereafter, the kneader was heated to 50 ° C. with warm water, and 95 g of glycidyltrimethylammonium chloride (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., water content 20% by weight, purity 90% or more) was added dropwise over 2 hours. Thereafter, when the mixture was further stirred at 50 ° C. for 3 hours, all the cationizing agent was consumed by high performance liquid chromatography (HPLC) analysis. Thereafter, the mixture was neutralized with acetic acid, the product was taken out of the kneader, washed with water-containing isopropanol (water content 15%) and acetone, and then dried under reduced pressure to obtain cationized cellulose as 140 g of a white solid. By elemental analysis and colloidal titration, the chlorine element content is 9.4%, the nitrogen element content is 3.7%, the substitution degree as a cationic group on cellulose is 0.71 per glucose unit, and the reaction selection to cellulose is selected The property was 96% (based on the cationizing agent). The results are shown in Table 2.

Comparative Example 1
The reaction is carried out in the same manner as in Example 1 except that highly crystalline powdery cellulose (cellulose powder KC Flock W-50 (S), crystallinity 74%, polymerization degree 500, manufactured by Nippon Paper Chemical Co., Ltd.) is used as cellulose. went. As a result, no residual unreacted glycidyltrimethylammonium chloride was observed by HPLC analysis, but the substitution degree as a cationic group on cellulose was 0.097 per glucose unit, and the reaction selectivity to cellulose was 13%. there were. The results are shown in Table 2.

Comparative Example 2
In a 2 L flask, 100 g of the highly crystalline powdered cellulose used in Comparative Example 1 was placed, and under a nitrogen atmosphere, 1500 ml of a 20% aqueous sodium hydroxide solution was added and immersed for 1 day. Furthermore, after stirring for 5 hours with a stirrer at room temperature, an excess aqueous sodium hydroxide solution was removed by filtration and squeezed to obtain about 200 g of alkali cellulose.
The obtained alkali cellulose was put into the 1 L kneader, and 500 ml of dimethyl sulfoxide was added and dispersed as a non-aqueous solvent. Subsequently, when 95 g of the glycidyltrimethylammonium chloride was added and reacted at 50 ° C. for 5 hours, the raw material glycidyltrimethylammonium chloride was all consumed. After neutralizing with acetic acid and distilling off the solvent, it was washed with hydrous isopropanol (water content 15%) and acetone and dried under reduced pressure to obtain 105 g of cationized cellulose as a white solid. The degree of substitution as cationic groups on cellulose was 0.015 per glucose unit, and the reaction selectivity to cellulose was only 2%. The results are shown in Table 2.

Example 2
As low-crystalline powdery cellulose, Example 1 was used except that 100 g of powdered cellulose (crystallinity 37%, polymerization degree 600) obtained according to Production Example 1 and 10 g of 48% sodium hydroxide aqueous solution were used. As a result, the raw material glycidyltrimethylammonium chloride was all consumed, the substitution degree as a cationic group on cellulose was 0.70 per glucose unit, and the reaction selectivity to cellulose was 94%. The results are shown in Table 2.

Example 3
Into the 1 L kneader, 100 g of amorphous cellulose (crystallinity 0%, polymerization degree 400) obtained according to Production Example 1 and 135 g of glycidyltrimethylammonium chloride were charged together and stirred at room temperature for 2 hours. did. Thereafter, the mixture was heated to 50 ° C. and dehydrated under reduced pressure of 2 to 10 kPa. As a result, the water content with respect to cellulose in the system was 9.6% by weight.
Next, 5 g of a 48% sodium hydroxide aqueous solution was added while sprayed, and the mixture was stirred as it was for 5 hours. As a result, all the raw material glycidyltrimethylammonium chloride was consumed by HPLC analysis. Then, after neutralizing with 1N hydrochloric acid, the product was taken out of the kneader, washed with hydrous isopropanol (15% water) and acetone, and dried under reduced pressure to obtain 188 g of a cationized cellulose as a white solid. By elemental analysis and colloidal titration, the elemental chlorine content is 11%, the elemental nitrogen content is 4.4%, the degree of substitution as cationic groups on cellulose is 1.00 per glucose unit, and the reaction selectivity to cellulose is 95%. Met. The results are shown in Table 2.

Example 4
Into the 1 L kneader, 100 g of amorphous cellulose (crystallinity 0%, polymerization degree 400) obtained according to Production Example 1 was added, 5 g of 48% sodium hydroxide aqueous solution was added, and 3 hours in a nitrogen atmosphere. Stir. Thereafter, the kneader was heated to 60 ° C. with warm water, and 230 g of the glycidyltrimethylammonium chloride was added dropwise over 3 hours while dehydrating in a pressure range of 5 to 10 kPa. After further stirring for 3 hours, about 15 g of water was distilled from the reaction system. 92% of the raw material glycidyltrimethylammonium chloride was consumed in the HPLC analysis. Neutralized with acetic acid as it was, and the product was taken out from the kneader, washed with water-containing isopropanol (15% water) and acetone to remove neutralized salts and unreacted substances, dried under reduced pressure, and 270 g of cationized cellulose. As a pale brown white solid. By elemental analysis and colloidal titration, the elemental chlorine content was 16%, the elemental nitrogen content was 6.4%, the degree of substitution as cationic groups on cellulose was 1.49 per glucose unit, and the reaction selectivity to cellulose was 91% Met.

Example 5
The reaction was carried out for 5 hours in the same manner as in Example 1 except that 500 ml of dimethyl sulfoxide was added as a solvent. As a result, the consumption amount of the raw material glycidyltrimethylammonium chloride was 90%, and thus the reaction was further carried out for 2 hours. As a result, all the raw materials were consumed, the substitution degree as a cationic group on cellulose was 0.69 per glucose unit, and the reaction selectivity to cellulose was 94%. The results are shown in Table 3.

Example 6
The reaction was carried out in the same manner as in Example 5 except that 500 ml of water-containing isopropanol (15% water) was used as a solvent. As a result, all the raw material glycidyltrimethylammonium chloride was consumed, and the degree of substitution as a cationic group on the cellulose was in glucose units. The reaction selectivity to cellulose was 50%. The results are shown in Table 3.

Example 7
600 g of amorphous cellulose (crystallinity 0%, polymerization degree 600) obtained in Production Example 1 and 10.9 g of sodium hydroxide were added to an agitated ball mill (Mitsui Mining Co., Ltd. Attritor), under a nitrogen atmosphere, It mixed using the steel ball (filling rate 30%). This was added to a 5 L kneader, heated to 70 ° C., and dehydrated under a reduced pressure of 10 to 20 kPa while adding 777.7 g of hydrated glycidyltrimethylammonium chloride (water content 20% by weight, purity 90% or more) over 10 hours. The solution was added dropwise and stirred for another 2 hours. As a result, all glycidyltrimethylammonium chloride was consumed by HPLC analysis. Thereafter, the mixture was neutralized with acetic acid, the product was taken out of the kneader, washed with water-containing isopropanol (water content 15%) and acetone, and then dried under reduced pressure to obtain cationized cellulose as 1.14 kg of a light brown white solid. By colloidal titration, the substitution degree as a cationic group on cellulose was 0.96 per glucose unit, and the reaction selectivity to cellulose was 96% (based on the cationizing agent). The results are shown in Table 2.

  From Table 2 and Table 3, Examples 1-7 can improve the reaction selectivity of a cationizing agent compared with Comparative Examples 1 and 2, and can obtain the cationized cellulose which has desired substitution degree efficiently. .

  According to the production method of the present invention, cellulose can be directly cationized industrially and with high selectivity, and the obtained cationized cellulose has a detergent composition such as shampoo, rinse, treatment, conditioner, etc. It can also be used in a wide range of applications such as compounding components, dispersants, modifiers, and flocculants.

Claims (6)

A process for producing a cationized cellulose represented by the following general formula (2), wherein low-crystalline powdery cellulose is reacted with a glycidyl trialkylammonium salt represented by the following general formula (1) in the presence of a catalyst.

(Wherein R ^{1 to} R ³ represent the same or different hydrocarbon groups having 1 to 4 carbon atoms, and X represents a halogen atom.)

(In the formula, R ⁴ represents a hydrogen atom or a cationic group represented by the following general formula (3), and R ⁴ does not become a hydrogen atom. N represents a number of 100 to 2000.)

(Wherein R ^{1 to} R ³ and X are the same as above).   The method for producing cationized cellulose according to claim 1, wherein the reaction is carried out in the presence of a catalytic amount of a catalyst.   The method for producing cationized cellulose according to claim 1 or 2, wherein the crystallinity of the low-crystalline powdery cellulose is 50% or less.   The manufacturing method of the cationized cellulose in any one of Claims 1-3 whose water content with respect to low crystalline powdery cellulose is 100 weight% or less.   The method for producing cationized cellulose according to any one of claims 1 to 4, wherein the low-crystalline powdery cellulose is reacted using a non-aqueous solvent of 10 times by weight or less.   The method for producing cationized cellulose according to any one of claims 1 to 5, wherein an alkali metal hydroxide is used as a catalyst.