JPS6261042B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel sulfoalkylcellulose ammonium salt and a method for producing the same. Conventionally, various types of water-soluble cellulose derivatives have been known, but they have various characteristics such as viscosity stability when water-soluble, stability or compatibility with acidic substances, polyvalent metal ions, surfactants, etc. Or, when made into a film, there are problems with heat resistance, ash content, etc., and in many cases, it is not able to fully demonstrate its function. As a result of intensive research by the present inventors to develop new cellulose derivatives, we found that sulfoalkylcellulose ammonium salts in which the average degree of substitution of sulfoalkyl ammonium groups per anhydroglucose unit is 0.2 or more (preferably 0.3 or more), (1) It is an easily water-soluble compound with excellent thickening and caking properties. (2) Aqueous solutions maintain stable viscosity even in the presence of acidic substances, polyvalent metal ions, etc., and do not cause precipitation or precipitation. (3) It has excellent compatibility with surfactants, etc., and (4) It leaves almost no ash even when fired. completed. The sulfoalkylcellulose ammonium salt of the present invention can be obtained as a sulfoalkylcellulose ammonium salt corresponding to the raw material sulfoalkylcellulose sodium salt by reacting the sulfoalkylcellulose sodium salt with an inorganic or organic ammonium salt. . For convenience, this reaction can be expressed as Cell-O(CH ₂ ) _o SO ₃ Na for sulfoalkylcellulose sodium salt, and the exchange reaction between sodium ions and ammonium ions proceeds at almost 100% reaction rate. do.

[Table] Monium salt
The sulfoalkylcellulose sodium salt used in the above reaction is one in which n is 1, 2 or 3, such as the sulfomethylcellulose sodium salt disclosed in U.S. Pat. No. 2,820,788. , Tietskoslovakia Patent No.
Sulfoethylcellulose sodium salt disclosed in No. 168,967, Makromolekulare Chemie 93
An example is the sulfopropyl cellulose sodium salt disclosed in No. 259. In order to obtain a sulfoalkylcellulose ammonium salt in which the average degree of substitution of sulfoalkyl ammonium groups per anhydroglucose unit is 0.2 or more, which is the object of the present invention, the raw material sulfoalkylcellulose sodium salt must be The average degree of substitution of the sulfoalkyl ammonium group is required to be 0.2 or more. In addition, as an inorganic or organic ammonium salt, X in the formula is C1, NO ₃ , (SO ₃ )〓, (SO ₄ )
Examples include inorganic or organic ammonium salts such as CH ₃ COO. The amount of ammonium salt to be used relative to the sulfoalkylcellulose sodium salt may be 5 to 30 moles per anhydroglucose unit of the sulfoalkylcellulose sodium salt. The reaction is carried out by mixing the sulfoalkylcellulose sodium salt and ammonium salt in a suitable medium and maintaining the temperature between about room temperature and 80°C while reacting at a temperature of about 0.2°C.
Completed by continuing stirring for ~4 hours,
A sulfoalkylcellulose ammonium salt is produced in which the sodium ions of the sulfoalkylcellulose sodium salt are replaced by ammonium ions. As the medium used in this reaction, it is preferable to use a water-water-soluble organic solvent mixed medium, and examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, and dioxane. It is desirable to do so. The mixing ratio of these organic solvents and water is
It is desirable to create a mixed system in which the ammonium salt as a reaction raw material is sufficiently dissolved, while the sulfoalkylcellulose ammonium salt as a product is not dissolved as much as possible, that is, the water content is 10 to 80% by weight. If it is less than 10% by weight, the ammonium salt will not be sufficiently dissolved and the reaction will not progress smoothly, while if it is more than 80% by weight, the viscosity of the reaction system will increase and the reaction operation will become difficult. After the reaction is completed, a water-soluble organic solvent is added as necessary to crystallize and recover the product with as little loss as possible. The crude product thus obtained is approximately 20% (by weight)
By washing with a water-containing water-soluble organic solvent to remove excess ammonium salt and by-product salt, and then drying, a white powdery sulfoalkylcellulose ammonium salt is obtained. The water-containing water-soluble organic solvent used for the above-mentioned cleaning is preferably a mixed solvent of water and a water-soluble solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, or dioxane, and the mixing ratio of water is 10 to 30%.
(Weight) It is desirable to keep it around. In addition, sulfoalkylcellulose sodium salt is alkali cellulose with a sulfoalkylating agent (sodium chloromethanesulfonate, sodium chloroethanesulfonate, propane sultone).
However, this reaction mixture can be subsequently subjected to a reaction to obtain a sulfoalkylcellulose ammonium salt without isolating the sulfoalkylcellulose sodium salt from the reaction mixture. That is, the pulp, sodium hydroxide, and sulfoalkylating agent are mixed in a water-soluble organic solvent (acetone,
A sulfoalkylcellulose sodium salt is produced by stirring and heating in isopropyl alcohol, etc.), and after neutralizing this reaction mixture with an acid, a predetermined amount of the above-mentioned inorganic or organic ammonium salt is added to it. In addition, room temperature ~
By continuing stirring for approximately 0.2 to 4 hours while maintaining the temperature at 80°C, a sulfoalkyl cellulose ammonium salt is obtained. The sulfoalkylcellulose ammonium salt of the present invention is a water-soluble compound and has the above-mentioned characteristics. It is suitably used as a binder in the industry, (3) a thickener for general aqueous liquids, and (4) the production of films, etc. Next, examples of the present invention will be given. Example 1 10 parts of powdered linter pulp (parts indicate parts by weight,
), 15.4 parts of a 44% aqueous sodium hydroxide solution and 100 parts of isopropyl alcohol were charged into a reactor, and the reactor was placed in a 5°C bath and stirred for 30 minutes. of the mixture was added, the bath temperature was raised, and the mixture was stirred under reflux conditions for 1 hour. After neutralizing excess sodium hydroxide with acetic acid, the reaction product was filtered, washed twice with 300 parts of a water-methanol mixed solvent containing 20% (by weight) water, and then heated at 60°C for 50 minutes. After drying for hours, 14 parts of sulfoethyl cellulose sodium salt having an average degree of substitution of sulfoethyl sodium groups of 0.4 was obtained. 10 parts of this sulfoethylcellulose sodium salt and 30 parts of ammonium chloride (which corresponds to 13 moles per anhydroglucose unit of the sulfoethylcellulose sodium salt) are mixed with 200 parts of a water-methanol mixed solvent containing 20% (by weight) of water. The mixture was reacted at room temperature for 1 hour with stirring. Next, the reaction product was collected, washed with a water-methanol mixed solvent containing 20% (by weight) water to remove excess ammonium chloride and by-product sodium chloride, and then dried at 60°C for 5 hours. As a result, white powdery sulfoethylcellulose ammonium salt was obtained with a yield of over 99%. The average degree of substitution of the sulfoethyl ammonium group was investigated based on the nitrogen analysis value by Kjeldahl method, and it was confirmed to be 0.4, and the results of infrared absorption spectrum analysis of this product are as shown in Figure 1. Ta. Example 2 17 parts of powdered linter pulp, 55 parts of 17% aqueous sodium hydroxide solution and 250 parts of isopropyl alcohol
After placing the reactor in a 5℃ bath and stirring for 30 minutes, 25 parts of propane sultone was added to it, and while stirring, the internal temperature was raised to about 40℃.
The reaction was carried out at ℃ for 6 hours. Then, after neutralizing excess sodium hydroxide with acetic acid, the reaction product was filtered, washed three times with a water-methanol mixed solvent containing 10% (by weight) water, and then dried at 60°C for 5 hours. As a result, 23 parts of sulfopropylcellulose sodium salt having an average degree of substitution of sulfopropyl sodium groups of 0.7 was obtained. This sulfopropyl cellulose sodium salt 10
and 40 parts of ammonium sulfate (which corresponds to 9.3 moles per anhydroglucose unit of the sulfopropylcellulose sodium salt) with 150 parts of a water-acetone mixed solvent containing 20% (by weight) of water;
The reaction was allowed to proceed at room temperature for 2 hours while stirring. Next, the reaction product was collected and thoroughly washed with the same water-acetone mixed solvent as above,
After drying at 60°C for 5 hours, a white powdery sulfopropyl cellulose ammonium salt was obtained with a yield of over 99%. The average degree of substitution of the sulfopropylammonium group was determined to be 0.7 based on the nitrogen analysis value by Kjeldahl method, and the results of infrared absorption spectrum analysis of this product were as shown in Figure 2. . Example 3 10 parts of powdered wood pulp, 10 parts of sodium chloromethane sulfonate, 43% aqueous sodium hydroxide solution
17.5 parts and 140 parts of isopropyl alcohol were placed in an autoclave and reacted at an internal temperature of 120°C for 1 hour (sulfomethylcellulose sodium salt was produced), then excess sodium hydroxide was neutralized with acetic acid and cooled to room temperature. . Next, 20 parts of water, 40 parts of isopropyl alcohol, and 30 parts of ammonium nitrate were added to this reaction mixture, and the mixture was stirred and reacted for 2 hours. The reaction product was collected, thoroughly washed with a mixed solvent of water and isopropyl alcohol containing 20% (by weight) water, and dried at 60°C for 5 hours.
It was obtained with a yield of more than %. The average degree of substitution of the sulfomethylammonium group was examined based on the nitrogen analysis value by Kjeldahl method, and it was confirmed to be 0.4.
The results of infrared absorption spectrum analysis of this product were as shown in FIG.

[Brief explanation of the drawing]

Figures 1 to 3 show the results of infrared absorption spectrum analysis of the sulfoalkylcellulose ammonium salts obtained in each example. Figure 1: Sulfoethylcellulose ammonium salt, Figure 2: Sulfopropylcellulose ammonium salt, Figure 3: Sulfomethylcellulose ammonium salt.

Claims (1)

[Scope of Claims] 1. A sulfoalkylcellulose ammonium salt having an average degree of substitution of sulfoalkyl ammonium groups per anhydroglucose unit of 0.2 or more. 2. Production of a sulfoalkylcellulose ammonium salt having an average degree of substitution of sulfoalkyl ammonium groups per anhydroglucose unit of 0.2 or more, which is characterized by reacting a sulfoalkylcellulose sodium salt with an inorganic or organic ammonium salt. Method.