JPS5915921B2 - Method for producing diethylaminooxypropylcellulose 1 and 2 - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving the quality of diethylaminooxypropylcellulose I and (2), which are derivatives of cellulose (1) and (2).

The above derivatives have basicity and are used in various fields of science and technology as ion exchangers for separation and purification of biochemical objects, complex salt-forming substances for metal purification and enrichment, catalysts, etc. .

The prior art has a maximum of 1.6 weight percent and 6.
Diethylaminooxypropylcellulose I and II, which are derivatives of cefrulose I and II, each containing 3 percent by weight of nitrogen, are known.

(For example, Noreika (R, M, No eika), Zdanavichus, (I, I, Zdanavichus) 5
Cellulose Chemical Industry (CelluloseChem)
Technol), 1971, 5, 117; Mongde (
G, Montgudet), ``paintures, ``pigments''
S. Vernis”), 1958, 34, 204, 27
1,9311: see French Patent No. 1,130,231).

However, the water vapor adsorption power of these cellulose I and II derivatives at a relative humidity of 63% and a temperature of 20°C is low;
The water vapor adsorption power of the derivative of cellulose I is less than 7.3 percent, and the water vapor adsorption power of the dielectric 5 conductor of cellulose I is less than 11 percent (adsorption power is calculated on the basis of air-dried cellulose weight). Also known are processes for the preparation of diethylaminooxypropylcellulose I and above, in which the cellulose is treated with diethylepoxypropylamine and the final product is subsequently purified (washed with water and extracted with an organic solvent).

In this known process air-dried cotton cellulose is treated with diethyl epoxypropylamine in the presence of water to produce diethylaminooxypropylcellulose, the nitrogen content of which diethylaminooxypropylcellulose I is 1.6. Less than percent by weight. −
On the other hand, diethylaminooxypropyl cellulose, a derivative of cellulose, is produced by treating alkaline cellulose treated with mercerized alkali with diethyl epoxypropylamine, and the nitrogen content of this cellulose derivative is less than 6.3% by weight. be.

A disadvantage of these known diethylaminooxypropylcellulose derivatives is that they have a structure that is not sufficiently accessible to water vapor.

Furthermore, these cellulose derivatives are colored to a considerable extent. An increase in water vapor sorption capacity, that is, an increase in the accessibility of water vapor to these cellulose I and its derivatives, diethylaminooxypropyl cellulose I, will further improve these products and also expand their field of application. Become.

A drawback of the known method for producing diethylaminooxypropyl cellulose derivatives is that the cellulose 1 derivative product obtained by the method is unable to adsorb more than 7.5 percent of water vapor (at a temperature of 20 and a relative temperature of 63 percent). ), and the inability of cellulose derivative products to sorb more than 11 percent of water vapor.

The water vapor sorption capacity of these cellulose derivatives is characterized by a strong dependence on the nitrogen content, similar to that found in the case of other cellulose derivatives (see, for example, ``Cellulose, Advances in Starch Chemistry'', 8 Advances in Starch Chemistry).
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An object of the present invention is to provide diethylaminooxypropyl cellulose, which is a cellulose 1 and n(7) derivative, which has a higher water vapor sorption ability.

Another object of the present invention is to provide diethylaminooxypropyl cellulose I which has high structural accessibility and high reactivity.

Furthermore, another object of the present invention is to provide the above-mentioned cellulose derivative having a low degree of coloration.

Another object of the present invention is to provide diethylaminooxypropylcellulose 1 having the above properties and a method for producing it. Cellulose I and HC of the present invention provided in accordance with these and other purposes! )P
! The i-conductor diethylaminoepoxypropyl cellulose I and (their nitrogen content is less than 1.6 weight percent for cellulose I structures and less than 6.3 weight percent for cellulose structures) have a high water vapor sorption capacity (temperature (at 20° C. and 63% relative humidity) is 7.5 to 14 percent for those with cellulose I structure, and 11.5 to 36 percent for those with cellulose structure.

These diethylaminoepoxypropyl cellulose derivatives provided by the present invention have the same nitrogen content as known cellulose derivatives, but have increased water vapor sorption capacity, higher structural accessibility, and higher reactivity. properties, such as high reactivity in acetylation reactions, low degree of coloration,
Furthermore, as mentioned above, it has the feature that it can be used in various fields of science and technology.

Among the above cellulose derivatives provided by the present invention, the most preferred ones have a nitrogen content of 1.6 and 6.6%, respectively.
Among cellulose I and diethylaminoepoxypropyl derivatives of cellulose, which is 3%, the water vapor gathering power is 14% in the case of cellulose I derivatives;
In the case of cellulose derivatives, 36% (temperature 20
℃ and 63 percent relative humidity).

Diethylaminoepoxypropylcellulose derivatives having improved properties as described above are produced by the method of the present invention. That is, the nitrogen content is 1.6 weight percent and 6.3 weight percent, respectively, and the temperature is 2.
It is produced by treating diethylaminoepoxypropyl cellulose I and derivatives with acetic acid or an aqueous solution thereof, such that the water vapor sorption capacity at 0° C. and 63 percent relative humidity is less than 7.3 percent and 11 percent, respectively. A suitable amount of acetic acid according to the invention is 0.1 mole or more per mole of diethylaminooxypropyl groups. diethylaminooxypropyl cellulose I and having a water vapor sorption capacity of 5.6 to 5.7 and 9 percent, respectively, and a nitrogen content of 1.6 and 6,3 percent by weight, respectively, at a temperature of 20° C. and a relative humidity of 63 percent; Preferably, the derivative is treated with acetic acid or aqueous acetic acid.

In addition, the raw material diethylaminooxypropyl cellulose derivative was added at 1 mol per mol of diethylaminooxypropyl group.
It is desirable to treat with an aqueous acetic acid solution or acetic acid corresponding to a molar or more amount of acetic acid.

If the final product resulting from treatment of the raw cellulose derivative with acetic acid or aqueous acetic acid solution is not used immediately, it should be washed with water to remove residual acetic acid;
It should then be dried at a temperature of 20-30°C. According to the invention, cellulose of various origins (e.g. natural cellulose, regenerated cellulose) or cellulose in any form, e.g. diethylaminooxypropyl cellulose derivatives in the form of fibers, paper, fabrics, threads, films, etc., can be prepared by acetic acid or acetic acid. Can be treated with an aqueous solution.

The diethylaminooxypropylcellulose derivative that can be treated in the present invention may be air-dried or moistened by known methods. An intermediate drying step can therefore be omitted. The method of the present invention for preparing the above-mentioned diethylaminooxypropyl cellulose I and derivatives with improved water vapor sorption capacity is realized as follows.

Diethylaminooxypropylcellulose I and its derivatives as raw materials are mixed with an acetic acid aqueous solution or acetic acid corresponding to an amount of at least 0.1 mole, preferably at least 1 mole of acetic acid per mole of diethylaminooxypropyl group.

When treating acetic acid or an acetic acid aqueous solution, in order to ensure that the cellulose raw material is uniformly wetted, the weight ratio of the liquid to the cellulose raw material may be appropriate, but the molar ratio of acetic acid to diethylaminooxypropyl groups should be 1:0.1 or more. should be kept. Since the acetic acid concentration used in cellulose raw material treatment does not play a decisive role in the water vapor sorption capacity of the final product, the acid concentration should be selected depending on the respective treatment conditions.

For example, if glacial acetic acid is used (to activate it as the reaction medium) and the final product is to be used as a starting material for further acetylation, the diethylaminooxypropylcellulose derivative can be processed with glacial acetic acid. Should.

In this case fresh glacial acetic acid should be used in the acetylation step.

If the final product is to be used in an aqueous medium, the diethylaminooxypropylcellulose derivative should be treated with dilute acetic acid, followed by a water wash to remove the acid. It is the concentration of acid that has the greatest substantial effect on the color of the final product. Table 1 provides data on various chromaticities of diethylaminooxypropyl cellulose derivative samples before and after treatment with various acetic acid concentrations. Compared to the nitrogen content of the raw diethylaminooxypropylcellulose derivative, treatment with acetic acid or aqueous acetic acid does not affect the nitrogen content of the resulting product.

The length of the raw cellulose derivative treatment time can vary from minutes to hours.

Longer treatment times do not affect the quality of the product obtained. The processing time is usually set according to actual operating conditions. If the final product prepared by treating the raw cellulose derivative with acetic acid or an acetic acid aqueous solution is not used immediately after preparation, the acetic acid should be washed with water and dried. It is preferable to carry out drying at 20 to 30°C. Drying at a higher temperature than the above-mentioned temperature has the effect of negating the water vapor sorption ability of the final product. For example, diethylaminooxypropyl cellulose prepared by treating air-dried cotton cellulose containing 1.6% by weight of nitrogen with diethyl epoxypropylamine in the presence of water and treated with acetic acid or aqueous acetic acid according to the present invention. If I is dried at room temperature, 14 percent of water vapor can be sorbed at a temperature of 20 DEG C. and a relative humidity of 63 percent; however, if the drying temperature is between 95 and 100 DEG C., only 5.6 percent of water vapor can be sorbed. As already mentioned, this method makes it possible to increase the reactivity of diethylaminooxypropylcellulose derivatives.

The data in Table 2 show that in acid acetylation reactions, there is a clear influence of acetic acid or acetic acid aqueous solution treatment on the reactivity of cellulose derivatives. The sample used was diethylaminooxypropyl cellulose prepared by aminating air-dried cotton cellulose with diethyl epoxypropylamine in the presence of 1 liter of water and containing 1.6 weight percent nitrogen. Some of the samples were treated with glacial acetic acid before acetylation, while other parts were acetylated without pretreatment with acetic acid. Acetylation of the sample was 1.6% (of sample weight) of free perchloric acid.
was carried out by a heterogeneous method in a benzene medium in the presence of Columns 2 and 3 of Table 2 have in the denominator the data obtained by acetylation of the sample not treated according to the invention, while the data in the numerator are obtained with the sample treated with glacial acetic acid. It is something that was given. To aid in understanding the present invention, examples of methods for preparing diethylaminooxypropyl cellulose I and derivatives with improved water vapor sorption capacity are described below.

In the following example, the water vapor sorption capacity is characterized from the equilibrium humidity l at a temperature of 20° C. and a humidity of 63 percent, and the humidity is calculated relative to the weight of the air-dried sample. Example 1 Yellow diethylaminooxypropylcellulose I with a nitrogen content of 1.6% by weight and an equilibrium humidity of 5.6-5.7% prepared by amination of air-dried cotton cellulose with dinityl epoxypropylene in the presence of water. was treated with glacial acetic acid in an amount of 300 moles of acetic acid per mole of diethyl-leaaminooxypropyl groups (liquid ratio 20).

The treatment operation was carried out at room temperature, and after the treatment, the product was washed with water until it became a neutral reaction and dried at room temperature. The resulting product was a white fibrous material containing 1.6 weight percent nitrogen and had an equilibrium humidity of 14 percent. Example
2,3,4 Diethylaminooxypropyl cellulose I derivatives with various nitrogen contents and equilibrium humidity of 5,5 to 6 percent,
It was prepared by aminating air-dried cotton cellulose with diethyl epoxypropylamine in the presence of water and then treated with a 10 percent aqueous acetic acid solution at a temperature of 25° C. and a liquid ratio of 20.

This reaction product was washed with water until it became a neutral reaction, and the temperature was 2.
It was dried at 5°C. Table 3 shows the nitrogen content of the raw material and the final product, the number of moles of acetic acid per mole of diethylaminooxypropyl groups (MACOH), and the equilibrium humidity of the product obtained. hya 0 #:ri:. Examples 5, 6, 7 Air-dried cotton cellulose was aminated with diethylaminooxypropylamine in the presence of water, containing 1.5 weight percent nitrogen and having an equilibrium humidity of 7.3 percent. and then treated with various acetic acid concentrations at room temperature and a liquid ratio of 20.

The final product was washed with water until the reaction became neutral, and the temperature was 25~25°C.
It was dried at 30°C. Table 4 shows the experimental data. The final product contained 1.5 weight percent nitrogen and had an equilibrium humidity of 13.9 percent. Example 8
, 9, 10, 11 diethylaminooxypropyl cellulose derivatives prepared by amination of cotton alkaline cellulose (16 percent sodium hydroxide) with diethyl epoxypropylamine in varying amounts of nitrogen and humidity,
Treated with a 20,10% liquid ratio acetic acid solution at room temperature.

The reaction product was washed with water until the reaction became neutral and dried at room temperature. Table 5 provides experimental data for nitrogen content of the feedstock and final product, moles of acetic acid per mole of diethylaminooxypropyl groups (MACOH), and equilibrium humidity of the feedstock and final product.

Examples 12, 13, 14 Diethylaminooxypropyl cellulose having an equilibrium humidity of 10 percent and containing 4.9 percent nitrogen by weight is aminated with cotton alkaline cellulose (20 percent sodium hydroxide) with diethyl epoxypropylamine. and then treated with various acetic acid concentrations at room temperature and a liquid ratio of 20.

The final product was washed with water until neutral reaction and dried at room temperature. Table 6 shows the experimental data. The final product contained 4.9 weight percent nitrogen and 34 percent humidity.

Example 15 Diethylaminooxypropylcellulose containing 11 percent humidity and 4.9 percent nitrogen was prepared by aminating viscous staple with diethyl epoxypropylamine in the presence of water, followed by aqueous acetic acid ( 1 mole of acetic acid per mole of diethylaminooxypropyl groups).

The liquid ratio was 20 and the treatment was carried out at room temperature. The final product was then washed with water until neutral reaction and dried at room temperature. The final product is 27 percent moisture and 4.9 percent nitrogen.
Includes weight percent. Examples 16, 17 Similar to those described in Examples 12, 13 and 14, diethylaminooxypropyl cellulose was treated with aqueous acetic acid solutions of various concentrations at room temperature and liquid ratio 10.

The reaction product was then washed with water until the reaction was neutral and dried at room temperature. Table 7 shows the experimental data.

Examples 18 and 19 below demonstrate that the reaction is improved after treating cellulose derivatives with acetic acid or aqueous acetic acid.

Example 18 Diethylaminooxypropylcellulose prepared as in Example 1 (except that the acetic acid was not washed off and not dried) was treated with benzene in the presence of perchloric acid by a known method. Acetylated in medium.

After replacing the spent acid with fresh glacial acetic acid and keeping the sample under conditions suitable for activation of cellulose with glacial acetic acid, crystalline violet was dissolved in glacial acetic acid in the presence of 0.1. The sample was titrated (neutralization of the amino groups) with normal perchlorine solution, then dehydrated and poured with 80 percent of the acetylation mixture containing 23.2 weight percent acetic anhydride and 76.8 weight percent benzene. The remaining 20 percent acetylation mixture was added together with perchloric acid as a catalyst. Perchloric acid was added in an amount of 1.6 percent of the sample weight. After 4 hours of acetylation at a liquid ratio of 44 and a temperature of 30° C., the perchloric acid was neutralized with a 10 percent potassium carbonate solution in glacial acetic acid and the product was washed with water. The final product contained 55.2 weight percent bound acetic acid (degree of hydroxyl conversion 0.96) and 0.8 weight percent nitrogen.
The solubility of the product in methylene chloride was 65.3 percent. Example 19 Diethylaminooxypropyl cellulose prepared as in Example 1 (except that a 10 percent acetic acid solution was used) was acetylated and activated as described in Example 18.

However, the addition of perchloric acid to the second portion of the acetylation mixture and condensation was carried out to perform two roles, namely the role of neutralizing agent for the amino groups and catalyzing the reaction. The final product is 55.2 weight percent combined acetic acid and 0 nitrogen.
．． The solubility of the product in methylene chloride, which contained 8 weight percent, was 71.0 percent.

Embodiments of the invention are summarized as follows.

1 Diethylaminooxypropylcellulose I and derivatives contain 1.6 or 6.3 weight percent nitrogen, respectively, and have water vapor sorption capacities of 14 and 36 weight percent, respectively, at a temperature of 20°C and a relative humidity of 63 percent The method described in item 1 of the scope.

2 Diethylaminooxypropylcellulose I and derivatives treated with acetic acid or aqueous acetic acid to give 1.6 or 6, respectively.

The method of claim 1, containing 3 weight percent nitrogen and having a water vapor sorption capacity of 5.6 to 5.7 and 9 weight percent, respectively, at a temperature of 20 DEG C. and 63 percent relative humidity.

3 Raw material diethylaminooxypropylcellulose I
The method according to claim 1 and claim 2, wherein the derivative is treated with an aqueous acetic acid solution or acetic acid corresponding to at least 1 mole of acetic acid per mole of diethylaminooxypropyl group.

4. After the acetic acid or acetic acid aqueous solution treatment, the diethylaminooxypropyl cellulose derivative is washed with water to remove acetic acid and dried at a temperature of 20 to 30° C. Method.

Claims (1)

[Claims] 1 Maximum water vapor adsorption capacity at relative humidity of 63% and temperature of 20° C. is 7.3% and 11%, respectively, and maximum nitrogen content is 1.6 and 6.3%, respectively.
Diethylaminooxypropyl cellulose I, a derivative of cellulose I and II, in weight percent
and II with acetic acid or an acetic acid aqueous solution corresponding to at least 0.1 mole of acetic acid per mole of diethylaminooxypropyl group, each having a maximum water vapor adsorption capacity of 7.5% at a relative humidity of 63% and a temperature of 20°C.
Diethylaminooxypropyl cellulose I and II, which are derivatives of cellulose I and II, with a content of 5 to 14 percent and 11.5 to 36 percent and a maximum nitrogen content of 1.6 and 6.3 percent by weight, respectively.
II manufacturing method.