JPH0772201B2 - Method for producing cationic hydroxyalkyl cellulose - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a coagulant, a pigment in the paper manufacturing industry, a preservative, an antistatic agent for fibers and woven fabrics, or a combination of cosmetics, shampoos, rinses, treatments and the like. The present invention relates to a method for producing a cationic hydroxyalkyl cellulose useful as an agent.

(Prior Art and Problems) As a method for producing a cationic hydroxyalkyl cellulose, the method described in Japanese Patent Publication No. 45-20318 has been generally known. In this method, cellulose is used as a reaction starting material, and an etherifying agent and a cationizing agent are sequentially or simultaneously added to carry out the reaction continuously, but the utilization rate of the etherifying agent and the cationizing agent is low and it is not economical. In addition, there are many unreacted substances and by-produced impurities, and there is a drawback that a great deal of labor is required to remove them.

Several production methods have been proposed since then, but it has been difficult to achieve a true effective utilization rate of the cationizing agent of 50% or more.

(Means for Solving Problems) In the present invention, the true effect of a cationizing agent is obtained by selecting the amount of unsubstituted glucose in the hydroxyalkyl cellulose used when cationizing the hydroxyalkyl cellulose under the production conditions of the hydroxyalkyl cellulose. The inventors have found that the utilization rate is improved and have completed the present invention.

(Object of the Invention) The present invention provides a method for producing a cationic hydroxyalkyl cellulose having good performance for various uses, in which an expensive cationizing agent is most effectively introduced into a hydroxyethyl cellulose skeleton. Is.

(Structure and Effect of the Invention) Regarding the method for producing a cationic hydroxyalkyl cellulose, Japanese Patent Application No. 60-274696 is very excellent as a method for producing it continuously from cellulose. By examining the reaction mechanism of hydroxyalkyl cellulose, it was found that the reaction of the cationizing agent with hydroxyalkyl cellulose during cationization is likely to occur at the hydroxyl group in unsubstituted glucose.

That is, in the method for producing a cationic hydroxyalkyl cellulose, the present inventor is characterized in that the amount of unsubstituted glucose in the hydroxyalkyl cellulose used when cationizing the hydroxyalkyl cellulose is 20 mol% or more. It is a method for producing hydroxyalkyl cellulose.

INDUSTRIAL APPLICABILITY In the present invention, hydroxyalkyl cellulose is used as a reaction starting material and then alkylated to obtain a hydroxyalkyl cellulose, which is cationized or hydroxyalkyl cellulose is cationized directly. When the amount of unsubstituted glucose in cellulose is 20 mol% or more, the effective utilization rate of the cationizing agent is remarkably improved. In addition, Japanese Patent Application Sho 60-274696
By carrying out the present invention according to the production method of No. 1, it is advantageous in terms of reactivity and economy.

For example, 8 to 15 times the weight of the lower aliphatic alcohol relative to the cellulose, specifically isopropanol, n-propanol, n-butanol, isobutanol, tertiary butanol, etc., a mixed medium of water and 1.0 per glucose residue of cellulose. ~ 1.5 mol times alkali metal hydroxide such as caustic soda and caustic potassium are used, and the ratio of the lower aliphatic alcohol to the total of the lower aliphatic alcohol and water is 85 to 90.
The cellulose is subjected to an alcerization treatment in a mixed medium having a composition of wt% to give an alkali cellulose, which is then reacted with an alkylene oxide to obtain a hydroxyalkyl cellulose.

At this time, it is necessary to select the conditions for hydroxyalkylation so that the amount of unsubstituted glucose becomes 20 mol% or more.

The hydroxyalkyl cellulose obtained in this way is subsequently fed into an alkali metal hydroxide in the reaction system, such as caustic soda,
Caustic potassium was added with a cationizing agent to adjust the amount of caustic soda at the end to 0.4 to 0.8 mol times per glucose residue of cellulose, and then lower aliphatic alcohol relative to the total amount of lower aliphatic alcohol and water in the reaction system. 50% alcohol
The cationic hydroxyalkyl cellulose is obtained by reacting with a cationizing agent in a mixed medium having a composition of about 100% by weight. By this method, the effective utilization rate of the cationizing agent is remarkably improved, and it has a performance applicable to various applications such as cosmetics, coagulants, pigments in the paper manufacturing industry, sizing agents, antistatic agents for fibers and fabrics. A cationic hydroxyalkyl cellulose can be easily obtained.

In the present invention, when starting the reaction from cellulose,
Prior to etherification, alcerization is performed with 1.0 to 1.5 mol times the alkali metal hydroxide, but the alkali metal hydroxide is 1.0
If it is less than the above, the amount of alcelization will not be sufficient,
The effective utilization rate of the etherifying agent becomes low. Further, if it is more than 1.5 mol times, a large amount of salt is generated by neutralization after the reaction is completed, not only a great deal of labor is required for its removal, but also the reactivity is improved,
It becomes difficult to raise the amount of unsubstituted glucose to 20 mol% or more. The etherification is followed by etherification, but the reaction temperature and reaction time must be carefully selected at this time.
That is, lowering the reaction temperature during etherification and reacting for a long time is effective for obtaining a uniform hydroxyalkyl cellulose, but is not suitable for obtaining a hydroxyalkyl cellulose for cationization. In this case, it is necessary to complete the hydroxyalkylation at 40 to 80 ° C, preferably 50 to 70 ° C, within 4 hours. Hydroxyalkyl cellulose obtained by this formulation contains 20 mol% of unsubstituted glucose.
As described above, the effective utilization rate of the hydroxyalkylating agent should be reduced.

The cationization reaction may be performed using a hydroxyalkyl cellulose obtained by the above method or a commercially available hydroxyalkyl cellulose having an unsubstituted glucose amount of 20 mol% or more, but in both cases, cationization is performed. The amount of alkali in the system at the end of addition of the agent is 0.
It is necessary to adjust it so that it is 4 to 0.8 mol times. At this time, the treatment differs depending on the type of the cationizing agent. That is, regarding the epoxide type, in the case of continuously reacting with etherification and cationization from cellulose, it is necessary to neutralize with an appropriate acid so that the amount of alkali in the system becomes 0.4 to 0.8 mol times before cationization. In the case of cationization from hydroxyalkyl cellulose, the cationization reaction is carried out after treatment with 0.4 to 0.8 molar amount of alkali metal hydroxide. When a secondary halohydrin type is used, it itself acts as a neutralizing agent, so when the reaction is initiated from cellulose, the amount of neutralizing agent used for partial neutralization before cationization is It is necessary to add it in consideration of the amount of the agent. The same applies when starting the reaction from hydroxyalkali cellulose.

In carrying out the present invention, when the reaction is started from cellulose, the amount is 8 to 15 times by weight, preferably 10 times as much as that of cellulose.
A mixed medium containing 14 to 14 times by weight of a lower aliphatic alcohol having 1 to 5 carbon atoms and water is used. When hydroxyalkylating, the ratio of the lower aliphatic alcohol to the total of the lower aliphatic alcohol and water is 85 to 90. % By weight, preferably 86-90
If it is not in weight%, not only the utilization rate of alkylene oxide will be low, but also the amount of unsubstituted glucose in the hydroxyalkyl cellulose will be changed, which will have a serious adverse effect on the subsequent cationization reaction.

The hydroxyalkyl cellulose having an unsubstituted glucose content of 20 mol% or more thus obtained is then cationized in the same system or in a separate system. At this time, the lower aliphatic alcohol and water in the cationization reaction are added together. It is necessary to adjust the composition such that the ratio of the lower aliphatic alcohol to 78 to 89% by weight, preferably 80 to 89% by weight. When the cationization reaction is carried out with a composition outside this range, not only the utilization rate of the cationizing agent is lowered, but also a cationic hydroxyalkyl cellulose having good performance cannot be obtained.

The cellulose used in the present invention may be any conventional cellulosic material such as chemical cotton, linter, wood, and pulp. However, in order to stir at a liquid ratio of 8 to 15 times by weight in a normal tank type reactor, it is desirable to use a cellulose fiber shortened by a cutting mill or the like.

As the alkylene oxide used in the present invention, ethylene oxide, propylene oxide and various butene oxides can be used. Also, by changing the addition amount of this alkylene oxide, it is possible to obtain hydroxyalkyl cellulose having various degrees of substitution. At this time, conditions such as reaction temperature and time are selected, and the amount of unsubstituted glucose is 20 mol%. You have to make it above.

As the cationizing agent used in the present invention, glycidyl trialkylammonium halide or its halohydrin type can be used. For example, glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl trimethyl ammonium bromide, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and the like.

After completion of the reaction, the remaining caustic soda is neutralized with a mineral acid or an organic acid, and then washed, purified and dried by a conventional method to obtain the desired cationic hydroxyalkyl cellulose. Further, at the time of neutralization, it is also possible to prevent so-called litter by adding an excess acid to adjust the pH to 5 or less and then adding glyoxal to crosslink.

(Examples) Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 42.6 g of pulp (containing 6.1% by weight of water) crushed with a cutting mill was placed in a separable flask, 32.8 g of water and 427.2 g of tertiary butanol were added to form a slurry, and 13.0 g of caustic soda was added to 20 g of water. The dissolved caustic soda aqueous solution was added, and the mixture was subjected to alcelization at 15 ° C for 1 hour while stirring. In this case, the ratio of the total tertiary butanol and water to cellulose is 12 times, and the ratio of the tertiary butanol to the total tertiary butanol and water is 88.5% by weight. Caustic soda is 1.32 moles per anhydroglucose unit of cellulose. After the alcelization, add 2.0 mol of ethylene oxide per anhydroglucose unit of cellulose and stir for 1 hour at 55 ℃.
The reaction was carried out for 0 minutes and further at 67 ° C. for 1 hour and 30 minutes. After cooling 3-
69.7 g of a 60% by weight aqueous solution of chloro-2hydroxypropyltrimethylammonium chloride was added, and the mixture was reacted at 55 ° C for 3 hours. After the reaction, the mixture was cooled, and the remaining caustic soda was neutralized with hydrochloric acid, and then dewatered, washed with 600 g of an acetone aqueous solution having an acetone / water ratio of 80/20 three times, and dried overnight at 60 ° C. This was purified by dialysis, and the completely desalted cationic hydroxyethyl cellulose after substitution with ethylene oxide had utilization rates of 1.43 and 71.5%, respectively, and an unsubstituted glucose amount of 3.06 mol% and a nitrogen content of 2.61%, the degree of cationizing agent substitution is 0.58, and the amount of unsubstituted glucose after cationization is 11.1 mol% 3-chloro-2hydroxypropyltrimethylammonium chloride effective utilization rate is 64%
The transparency of the 2 wt% aqueous solution was 560 mm or more.

Example 2 After obtaining an alkali cellulose in the same manner as in Example 1, ethylene oxide was added so that the amount of 3.0 mol per anhydroglucose residue of cellulose was added, and the mixture was heated at 55 ° C. for 1 hour 30 minutes at 69 ° C.
The reaction is carried out for 1 hour and 30 minutes to obtain hydroxyethyl cellulose.

Subsequently, 3-chloro-2hydroxypropyltrimethylammonium chloride was added to the cellulose in an amount of 0.9 mol per anhydrous glucose unit, and the mixture was reacted at 55 ° C. for 3 hours.
Of the obtained cationic hydroxyalkyl cellulose,
The degree of substitution of ethylene oxide is 2.0, the utilization rate is 66.7%, the amount of unsubstituted glucose is 20.8 mol%, and the nitrogen content is
2.27%, degree of cationizing agent substitution is 0.53, the amount of unsubstituted glucose after cationization is 8.1 mol%, effective utilization rate of cationizing agent is 58.9%, transparency of 2% by weight aqueous solution is 560 mm
That was all.

Comparative Example 1 42.6 g of pulp was slurried in the same manner as in Example 1, caustic soda was added so as to be 1.4 mole times per anhydrous glucose unit of cellulose, and the mixture was alcelized at 15 ° C. for 2 hours, and then 32.6 g of ethylene oxide was added, 2 hours 30 at 45 ℃
And reacted at 65 ° C. for 1 hour and 20 minutes. After cooling 3-chloro-2
Hydroxypropyltrimethylammonium chloride with 0.98 mole of anhydrous glucose unit in cellulose was added 55
Reaction was carried out at 0 ° C. for 3 hours to obtain cationic hydroxyethyl cellulose. The degree of substitution and utilization of ethylene oxide of the obtained cationic hydroxyethyl cellulose was 2.03.
And 67.7%, the amount of unsubstituted glucose is 19.5 mol%, 3-
Chloro-2-hydroxypropyltrimethylammonium has a degree of substitution, a nitrogen content and an unsubstituted glucose content of 0.
40%, 1.80% and 9 mol%, the effective utilization rate is 4
0.8%, and the transparency of the 2 wt% aqueous solution was 560 mm or more.

Example 3 40 g of 25 mol% hydroxyethyl cellulose (degree of substitution = 2.3) of unsubstituted glucose was dispersed in 182.2 g of 95.5 wt% tertiary butanol, and 7.8 g of caustic soda was dissolved in 14 g of water to which an aqueous solution of caustic soda was added. Then, the mixture was stirred at room temperature for 1 hour.
After that, 42.8 g of a 60% by weight aqueous solution of 3-chloro-2hydroxypropyltrimethylammonium chloride was added, and cationization was carried out at 55 ° C. for 3 hours. The cationized hydroxyethyl cellulose thus obtained was washed 4 times with 80% by weight acetone and completely desalted by dialysis. The degree of cationization and nitrogen content were measured to be 0.53% and 2.16, respectively.
%, The effective utilization rate of the cationizing agent is 58.9%, and 2
The transparency of the weight% aqueous solution was 560 mm or more.

Comparative Example 2 When 40 g of hydroxyethyl cellulose (substitution degree = 2.3) having an unsubstituted glucose amount of 14 mol% was reacted with the same formulation as in Example 3, the cationization degree and the nitrogen content of the obtained cationized hydroxyethyl cellulose were 0.44 each
%, 1.88%, the effective utilization rate of the cationizing agent was 49%, and the transparency of the 2 wt% aqueous solution was 560 mm or more.

Each analysis method will be described below.

1. Nitrogen analysis The Termulene method was adopted using a digital total nitrogen analyzer manufactured by Mitsubishi Kasei.

When hydrogen is flowed in the reaction tube and N-containing material is put therein, it is vaporized and decomposed and catalytically reduced to NH ₃ .

Other products are removed and NH ₃ is sent to the coulometric triangulation.

NH in the appropriate amount section₃+ H₂O → NH_Four + OH Next to this OH To H To determine the nitrogen content.

2. Measurement of degree of substitution of ethylene oxide on cationic hydroxyethyl cellulose The following Morgan method was adopted.

Hydroxyalkyl cellulose _{(RCell-O-CH 2 CH} 2 O
H) is reacted with hydrogen iodide (HI) as shown in formula (1).

R Cell-O-CH ₂ CH ₂ OH ＋ 3HI → R CellI ＋ ICH ₂ CH ₂ I ＋ 2H ₂ O …… (1) ICH ₂ CH ₂ I → CH ₂ ＝ CH ₂ ＋ I ₂ …… (2) ICH ₂ CH ₂ I ＋ HI → CH ₃ CH ₂ I + I ₂ (3) CH ₂ = CH ₂ + HI → CH ₃ CH ₂ I (4) Although the formula (1) occurs as the main reaction, the iodoethylene (I CH ₂ CH ₂ I) quantitatively reacts with deiodine (I ₂ ) and hydroiodic acid (HI) as in formulas (2) and (3) to produce iodine (I ₂ ). Iodoethyl (CH ₃ CH
₂ I) is the final product as shown in formula (4), but it goes out of the system without being absorbed by silver nitrate (AgNO ₃ ) and bromine water (Br ₂ ) aqueous solutions.

Collection and quantification of iodine (I ₂ ) ... Side chain -CH ₂ CH ₂ OH 1 mole of I ₂ can be collected from 1 mole of I ₂ in AgNO ₃ ethanol solution, and residual AgNO ₃ is removed with NH ₄ CHS. Titrate. The chemical reaction in this case is shown below.

I ^- In _{AgNO 3 + NH 4 CNS → AgCNS} + NH 4 NO 3 the collection of ethylene and quantification CH ₂ = CH ₂ was collected with Br ₂ solution and acetic _{^{Ma 2 S 2 O 3 - +}} AgNO 3 → AgI ( precipitate) + NO ₃ Residual Br ₂
Titrate. The chemical reaction in this case is shown below.

_{CH 2 = CH 2 + Br 2} → BrCH 2 CH 2 Br Na 2 S 2 O 3 + 4Br 2 + 5H 2 O → Na 2 SO 4 + 8HBr + H 2 SO 4 3. hydroxyethylcellulose substitution degree and calculation method hydroxyethylcellulose cationizing agent substitution degree When the degree of substitution is X, the degree of cationizing agent substitution is Y, and the content of hydroxyethyl cellulose is A (%) [determined from the degree of substitution of ethylene oxide of the above-mentioned two-cationic hydroxyethyl cellulose] and the content of cation group is B (%) If B is replaced by nitrogen content C (%) [1. Obtained from the nitrogen analysis method described above], 14 / 151.5 is multiplied to both sides of the equation (2) to obtain the equation (3).

X and Y are calculated from the equations (1) and (3).

4. Utilization rate Calculated based on the above 3.

(Effect of the invention) The present invention is a method for industrially very advantageous production of cationic hydroxyalkyl cellulose capable of significantly reducing the usage rate of expensive cationizing agents, and the cationic hydroxyalkyl cellulose obtained by this method is used. Alkyl cellulose is useful as a cosmetic, a coagulant, a pigment in the papermaking industry, a sizing agent, an antistatic agent for fibers and woven fabrics, etc. because it has good transparency and excellent antistatic properties.

Claims (1)

[Claims] 1. A cationic hydroxyalkyl wherein the amount of unsubstituted glucose in the hydroxyalkyl cellulose used when cationizing the hydroxyalkyl cellulose in the method for producing a cationic hydroxyalkyl cellulose is 20 mol% or more. Method for producing cellulose.