DE2433633C2 - Diethylaminohydroxypropyl celluloses of structure I or II and processes for their preparation - Google Patents

Description

The invention relates to diethylaminohydroxypropyl celluloses of structure I or II and processes for their preparation.

The above-mentioned ethylaminohydroxypropyl celluloses have the properties of bases and can be used as ion exchangers, for example for separation, isolation and cleaning of biochemical objects, as complexing agents, for example for cleaning and concentrating of metals, as catalysts, etc.

They are diethylaminohydroxypropyl celluloses made from cellulose of structure I or 11 known, which at most .1.6 Ciew -Λ. or a maximum of 6.3% by weight nitrogen accordingly contain the structural modifications mentioned (see, for example, R. M. Noreyka. 1. I. Sudanavchus. Cellulose Chem. Technol. 1971. 5. 117; Montegudei G. Pelniures. Pigments, vernls. I9S8. 34, 204fr. 271 ff. 311 ff; FR-PS Il 30 231). The ability of said celluloses of structure I. to sorb water vapor. amounts to a maximum of 7.3%, that of the Structure II at most 11% at a temperature of 20 * C and a relative humidity of 63% (the size of the sorption is calculated based on the Weight of air-dry cellulose)

There are also methods from the publications mentioned for the production of the above-described Dläthyläffilnohydroxycellulosen from cellulose of structure I or II by treating cellulose or alkali cellulose with Dietylepoxlpropylamln and subsequent cleaning of the end product (washing with water and extraction with organic solvents). In the process mentioned gives diethylamine hydroxypropyl celluloses of structure I, which contain at most 1.6 wt .-% nitrogen, by treating air-dry BuildnwoUcelluloses with diethyl epoxypropylamine in the presence of water and the diethylaminohydroxypropyl celluloses of structure IL, which contain at most 63% by weight nitrogen, by the treatment of alkali cellulose !! with diethylepoxipropylamine.

A disadvantage of the known DiethylaminohydroxypropyiceUulosen is the insufficient structural accessibility of the reactants. The accessibility

ία is determined by water vapor absorption. aside from that the celluloses mentioned are significantly discolored.

An increase in the maturity of sorbing water vapors, and accordingly the availability of diethylaminohydroxypropyl celluloses made of cellulose both the

IS Structure I as well as Structure II would make it possible to improve the quality of the products mentioned as well as to expand their area of use.

A disadvantage of the known methods li-t producing Diäthylaminohydroxypropylcellulosen it is that they do not allow it. To obtain products which sorb at a temperature of 20 ° C and a relative humidity of 63% but 73% water vapor, in the case of the celluloses of the structure I. and over 11% in the case of the celluloses of the structure H. The ability of said celluloses. Sorbing water vapor is extremely dependent on the nitrogen content. This dependence is also observed in other celluloses (see, for example, "Advances in the chemistry of cellulose and starch" edited by J. Honiman, Verlag der foreign

Literature. Moscow. 1962, page 335, in Russian).

The purpose of the present invention is to avoid the disadvantages mentioned.

The invention is based on the object. Manufacture diethylaminohydroxypropyl celluloses from cellulose of structure I and H, the increased ability to sorb water vapor. be more responsive and less colored, and develop a process for their manufacture.
This aurage is achieved in that Dläthylaminohydroxypropylcellulosen are made from cellulose of structure I or II, which contain a maximum of 1.6 wt .-% nitrogen in the case of structure I and a maximum of 6.3 wt% nitrogen t in the case of structure II, and that your ability. To sorb water vapor. 7.5 to

«14%. in the case of structure 1. and 11.5 to 36%. in the event of of structure II, at a temperature of 20 * C and one relative humidity of 63%.

The diethylamine hydroxypropyl celluloses according to the invention. the increased ability to have water vapor with the same content (compared to the known cases) to sorb in nitrogen are achieved by a high lugängllchkelt. increased responsiveness, for example both. Acelyllerung, decreased coloration and can, as mentioned above. In different

»Find use in areas of science and technology.

Particularly preferred diethylamine hydroxypropyl celluloses are those of structure I. which contain 1.6% by weight of nitrogen and which can sorb 14% water vapor, and structure II. Which contain 6.3% by weight of nitrogen and which can sort 36% water vapor, each at a temperature of 20% ° C and a relative humidity of 63%.
The Dläthylamlnohydroxypropylcellulosen with the properties described above are obtained according to the invention by Dläthylamlnohydroxypropylcellulosen of structure I, which contain a maximum of 1.6 wt .- * nitrogen and which contain a maximum of 73%

I water vapor at a temperature of 20 ° C and one j relative humidity of 63% can sorbleren and the 'by treating with cellulose with diethylepoxipropylamin have been obtained in a known manner, or the structure II, which contain a maximum of 6.3 wt .-% nitrogen and the maximum 11% water vapor at a temperature of 20 ° C and a relative humidity of 63% can sort and that by treating Alkali cellulose with diethyl epoxypropylamine in known Manner have been obtained with at least 0.1 mol acetic acid or its aqueous solutions per mole Dläthylaminohydroxypropylgruppen treated and the products obtained, if not immediately after Used for manufacture, washed with water and dried at a temperature of 20 to 30 ° C.

It is expedient to treat with acetic acid or the aqueous solutions of diethylaminohydroxypropyl celluloses from cellulose of the Stnikur I or II. the 1.6% by weight or 6.3% by weight of nitrogen corresponding to those mentioned Structures contain and have the ability to absorb 5.6 to 5.7 or 9% water vapor at a temperature of 20 ° C and a relative humidity of 63% according to the structures mentioned.

The starting diethylaminohydroxypropyl celluloses are expediently treated with acetic acid or its aqueous solutions in an amount of at least 1 mole of acetic acid per 1 mole of diethylamine hydroxypropyl groups.

In the case where by the treatment of the starting Oiäthylaminohydroxypropylcellulosen products obtained with acetic acid or its solutions are not used immediately after their preparation, the Acetic acid removed by washing with water and that product obtained is then dried at a temperature of 20 to 30 ° C. »

According to the invention, diethylaminohydroxypropyl cellulose materials can be used for the treatment of any origin (e.g. from native or regenerated cellulose) and any shape (fibers, paper, fabric, yarn, Films, etc.). The treatment of air-dry diethylamine hydroxypropyl cellulose materials can be used as well as cellulose materials in the wet state, which are made according to the known processes have been obtained. In the latter case, this becomes the stage of intermediate drying avoided.

The process for the production of Dläthylamlnohydroxypropylcellulosen made of cellulose of structure I or II, which have increased ability. To sorb water vapor, is carried out as follows.

The starting diethylamine hydroxypropyl celluloses made from cellulose of structure I or II are treated with acetic acid or their aqueous solution in an amount of at least 0.1 mol, preferably at least 1 mol, Acetic acid per 1 mole of diethylamine hydroxypropyl groups wetted. When treating the starting diethylamine hydroxypropyl celluloses Any weight ratio of liquid to cellulose material can be used Depending on the most uniform possible Wetting of the material can be applied, the molar ratio of acetic acid to the diethylaminohydroxypropyl groups, as stated above, is at least 0.1: I.

The concentration of acetic acid used is dated Viewpoint of the ability of the products obtained, * 5 Water vapor to sorblereVi, not decisive and one chooses them starting from the particular technological Considerations.

For example, if the product obtained is used as a starting material for a subsequent Acetylferung under Use of glacial acetic acid used as reaction medium The treatment of diethylamine hydroxypropyl celluloses is expediently carried out with glacial acetic acid. It is advisable to replace the used acetic acid with fresh before the acetylation. If the product obtained is to be used in aqueous media, the treatment is expediently carried out of diethylaminohydfoxypropylcelluloses ctarch Dilute with acetic acid solutions and then wash the product from the acid with water.

The concentration of acetic acid has a particularly important influence on the color of the obtained Products from. Table 1 contains information about the coloring of various samples of the diethylaminohydroxypropyl celluloses before and after their treatment with acetic acid of various concentrations.

Table 1

conditions Stick Color of the sample after after the amination material without Treat Treat the cotton salary, Treat ment with ment with cellulose in ment with 2% er Glacial acetic acid with diethyl Wt% vinegar more watery epoxipropylamine acid vinegar acid solution

In present
of 20%
NaOH
at 95 ° C
In present
of 20%
NaOH
at 95 ° C

In present
of water
at 60 ⁰ C

In present
of water
at 95 ° C

2.8 brown yellow light yellow

1.4 light brown - white

1.0 light yellow white

1.6

yellow light yellow white

Treatment with acetic acid or its aqueous solutions changes the nitrogen content in the obtained Products, compared to the starting diethylamine hydroxypropyl cellulose, not.

The duration of the treatment of the starting diethylaminohydroxypropyl celluloses can vary from a few minutes to a few hours. An increase in Duration does not affect the quality of the products obtained. The duration of treatment is usually starting from chosen by the specific technological considerations.

If by treating the starting Dläthylamlnohydroxypropylcellulosen products obtained with acetic acid or its aqueous solutions directly

After they are not used, they are washed with water by the acetic acid and dried. The drying is carried out at a temperature of from 20 to 30 ^° C. An increase in the drying temperature above the stated range affects the ability of the products obtained. To sort out water vapor, negative. For example, the diethylaminohydroxypropyl cellulose of structure I, which is obtained by treating the air-dry cotton cellulose with diethyl epoxypropylamine in the presence of water and contains 1.6% by weight of nitrogen, absorbs 14% water vapors after the treatment according to the invention and drying at room temperature a temperature of 2 ° C and a relative humidity of 63 ° .. while after the drying of the product mentioned, according to the present invention, at a temperature of 95 to 100 ° C, its ability to sorbleren water vapor under the conditions mentioned above, only still S to 6%.

Further processing:

As stated above, the proposed method makes it possible to use biäthyiaminohydroxypropylcellulosen with increased responsiveness. The information given in Table 2 is evidence of the positive influence of treatment with acetic acid or its aqueous solutions on the reactivity of the diethylaminohydroxypropyl celluloses in a subsequent acetylation. The investigations were on samples of the diethylaminoh / droxypropylcellulose carried out from cellulose of structure I, which contains 1.6% by weight of nitrogen and which is obtained by amination of air-dry cotton cellulose with di-stylepoxylpropylamine have been obtained in the presence of water. Part of the rehearsals were submitted the acetylation one treatment with acetic acid, while the other part without pretreatment with acetic acid was acetylated. The acetylation of the samples was carried out according to the heterogeneous method in the medium of benzene Carried out in the presence of 1.6% (based on the weight of the sample) tertiary excess chloric acid. In the Columns 2 and 3 of Table 2 are entered in the counter information that is used in the acetylation of samples were obtained that had not been subjected to the treatment according to the invention, and in the denominator information, obtained during the acetylation of the samples after their pretreatment with glacial acetic acid.

Table 3

Iron binding sheets from
Diethylaminohydroxypropyl celluloses *)

N content Exchange capacity Sorption capacity inventive in the in relation mg / g more appropriate Product, on the anions, better known Ions Wt% mg equivalent / g Ions exchanger calculated found exchanger 67 (D 130 0.4 0.24 0.24 12th 370 1.0 0.71 0.57 15th 3.3 2 ^ 37 2.3 13th

Table 2

Acetylation Salary of Solubility of duration, min acetylated samples acetylated samples to bound in methylene chloride, Acetic acid, wt% %

53.0 / 54.3
53.6 / 55.2

26.7 / 47.3 28.7 / 65.3

From the following Table 3 it can be seen that the invention Diethylamine hydroxypropyl celluloses improved ion exchange properties compared to the prior art heslt / en.

*) The sorption of the iron ions took place at a temperature of 25 "C and a pH value of 4 for 20 minutes from Fe CIj solutions from a concentration based on Fe (UI) 2,000 mg / l. The flow rate during sorption was 500. The source of literature is R. M. Noreika, I. I. Sd> -> awiuchus, Cellulose Chetn Techno! .. 1971. 5.117

For a better understanding of the present invention, the following examples of the preparation of Diethylaminohydroxypropyl celluloses from cellulose of structure I or II, which have increased ability. What to sorb water vapor. is mentioned in the examples the ability of celluloses to absorb water vapor, by equilibrium humidity at a temperature of 29 ° C and a relative humidity of 63%. calculated on the weight of the air-dry sample, labeled.

example 1

Diethylaminohydroxypropyl cilulose of yellow color of structure I with a nitrogen content of 1.6% by weight and an equilibrium moisture content of 5.6 to 5.7%. obtained by amination of the air-dry cotton cellulose with diethyl epoxypropylamine in the presence of Water, treated with glacial acetic acid, in the ratio of 300 moles of acetic acid per 1 mole of diethy.'jminohydroxypropyl groups (The liquor ratio was 20. This means the ratio of the volume to the treatment solution used to unit weight of the cellulose material to be treated). The treatment was carried out at room temperature, after which the product was washed with water until neutral and dried at room temperature. A fiber material of white color with a nitrogen content was obtained of 1.6% by weight and an equilibrium strength of 14%.

Examples 2 to 4

Dläthylaminohydroxypropylcellulosen from cellulose of structure I with different nitrogen content and an adhesive moisture content of 5.5 to 6%. obtain by amination of the air-dry cotton cellulose with diethyl epoxypropylamine in the presence of water, treated with 10% aqueous solution of Acetic acid at a liquor ratio of 20 and a temperature of 25 ° C. Then the products were bis washed with water to neutralize the reaction and dried at a temperature of 25 ° C. The information about the nitrogen content in the

and the products obtained, the amounts of acetic acid in moles (M ₁ ,,,,;) per 1 mole of diethylaminohydroxypropyl groups and the equilibrium moisture content of the products obtained are shown in Table 4.

Tabel No. nitrogen

the salary,

Example% by weight Table 4

No. of
Example

Equilibrium humidity,%

the after the

Starting treatment products with acetic acid solution

Nitrogen content,
Weight · /,
Output compound

0.3
0.7
1.6

Vl AiOH Equilibrium humidity of the product, received after the treatment with vinegar acid solution,% 157 7.8 67 11th 20th 14th

10

15th

8th 0.2 9 2.2 10 3.8 Ii 6.3

238
21
12th

7.4

11th

10.8
10
9

11.5
20th
27
36

Examples 5 to 7

Diethylaminohydroxypropyl cellulose from cellulose der Structure I with a nitrogen content of 1.5 wt. Λ, and an equilibrium moisture content of 7.3%. obtained by amination of the air-dry cotton cellulose with diethylepoxipropylamine In the presence of water, one treated with acetic acid of various concentrations. tion at a liquor ratio of 20 and room temperature. Then the product was up to the neutral table

Reaction washed with water and at a temperature

door dried at 25 to 30 ° C. The test conditions No.

Genes are listed in Table 5 (M ₁ ,,,,, = Lssigsüure- «of the example amount in moles).

Examples 12-14

Dilthylaminohydro.xypropylcellulose from cellulose of the structure II with a nitrogen content of 4.9% by weight, and an equilibrium moisture content of 10% by amination of cotton alkali cellulose (20% NaOIi) with diethylepoxlpropytamine treated one with acetic acid of various concentrations at a liquor ratio of 20 and room temperature. Then the product was washed with water until neutral and dried at room temperature. The experimental conditions are given in Table 7 (M,,. "= Amount of acetic acid in moles).

concentration
of acetic acid,%

Table 5

of the example

concentration
of acetic acid,%

M,

12th

13th

40

10
100 (glacial acetic acid)

95

2
10
100 (glacial acetic acid)

6.2
31
310

The treatment described gave a product with a nitrogen content of 1.5% by weight and an equilibrium strength of 13.9%.

Examples 8 to II

Diethylaminohydroxypropyl celluloses from cellulose of structure II with different nitrogen contents and different equilibrium humidity, obtained by amination of cotton alkali cellulose (16% NaOH) with diethyl epoxypropylamine, treated with 10% aqueous solution of acetic acid at a ^Μ liquor ratio of 20 and room temperature. Then the products were washed with water and dried at room temperature. The information on the nitrogen content in the starting materials and the products obtained, the amount of acetic acid in MoI Wi _ttOH ) per 1 mole of diethylaminohydroxypropyl groups and the equilibrium moisture content of the starting materials and the products obtained are given in Table 6.

The treatment described gave a product with a nitrogen content of 4.9% by weight and an equilibrium moisture content of 34%.

Example 15

Diethylaminohydroxypropyl cellulose from cellulose der Structure II with a nitrogen content of 4.9% by weight and an equilibrium moisture content of 11% was obtained by amination of viscose rayon with diethyl epoxypropylamine in the presence of water, treated ms /, with 2% aqueous solution of acetic acid, in a ratio of 1 mole of acetic acid per 1 mole of Dläthylaminohydroxypropylgruppen. The treatment was carried out at a liquor ratio of 20 and room temperature, after which the product is washed with water until neutral and at room temperature was dried. A product was obtained with a nitrogen content of 4.9% by weight and an equilibrium moisture content of 27%.

Examples 16 and 17

Diethyiamlnohydroxypropylcellulose was subjected to, analogously to that described in Examples 12 to 14, a treatment with acetic acid of various concentrations at a liquor ratio of 20 and room temperature. Then the product was

len reaction washed with water and at room temperature dried. The conditions and results of the tests are given in Table 8 (M ,,,, // = Amount of Uacetic Acid In Mol).

Table 8

Kr des concentration M _Ac0H Equilibrium Example the aqueous humidity Acetic acid,% of the product, received after the treatment with vinegar acid solution,% 16 1.2 0.6 23 17th 0.17 0.1 12th

10

15th

20th

In Examples 18 and 19 the increased reactivity of cetlulose confirmed after its treatment with acetic acid or its aqueous solutions.

Further processing:
Example 18

a) Acetification of a not treated with acetic acid Diethylaminohydroxypropyl cellulose

The diethylaminohydroxypropyl cellulose obtained according to Example 1 (However, without washing from the acetic acid and drying) one acetylated according to the known method (the literature source is Dlmov K., Laleva V., Chimija I Industrlja, 1966, 38, 407, in Bulga-

30 risch) to heterogeneous acetylation in the medium of benzene in the presence of superchloric acid. After replacing the used glacial acetic acid with fresh and painting the sample under the conditions generally assumed for the activation of the cellulose with glacial acetic acid, the sample was titrated with 0.1 η solution of superchloric acid in glacial acetic acid in the presence of crystal violet (neutralization of the amino groups), PRELITE from and golJ 8O '\> of the mixture to acetyllerenden consisting of 76.8 parts by weight ¹ N, benzene and 23.2 wt .-' \. Acetic anhydride. The remaining 20% of the acetylating mixture was added as a catalyst (chlorosilurc in an amount of 1.6% by weight based on the weight of the sample. After acetylation for 4 hours at a temperature of 30 ° C. and a liquor solution of 44, neutralization of the overchloric acid with 10% solution, a product was obtained which contains 55.2% by weight of bound acetic acid (the degree of conversion of the hydroxyl groups is 0.96) and 0.8% by weight of nitrogen. The solubility ties product in Müiriy'enchlorld is 65.3%.

b) Acetylation of a diethylamine hydroxypropyl cellulose treated with acetic acid

The one obtained according to Example I (but using a 10% aqueous solution of acetic acid) Dläthylamlnohydroxypropylcellulose was activated and acetylated according to the in Example 18 described Method, but with the addition of the second portion of the acetylated mixture of superchloric acid both for Neutralization of the amino groups as well as to catalyze the reaction. A product was obtained which 55.2 Wt .-% bound acetic acid and 0.8 wt .-% nitrogen contains. The solubility of the product in methylene chloride is 71.0%.

Claims (2)

Patent claims: 1. Process for the preparation of diethylaminohydroxypropyl celluloses of structure I, which are at most 1.6, or IL. soft at most 63 wt .-% nitrogen and wherein the derivatives of cellulose of structure I 7.5 to 14% and the derivatives of cellulose of structure II UJS to 36% water vapor at a temperature of 20 ° C and a relative humidity of 6i Sort% , characterized in that diethylaminohydroxypropyl celluloses of structure I which contain a maximum of 1.6% by weight nitrogen and which contain a maximum of 73% water vapor at a temperature of 20 ° C. and a relative humidity of 63% and which can be sorbleren by treating cellulose have been obtained with diethylepoxipropylamln in a known manner, or the structure II. which contain a maximum of 63 wt .-% nitrogen and which can sorb a maximum of 11% water vapor at a temperature of 20 ° C and a relative humidity of 63% and which by treatment of alkali cellulose with diethyl epoxypropylamine have been obtained in a known manner, with at least 0.1 mol of acetic acid or its aqueous solutions pr o Mol Ciäthrlaminohydroxypropylgruppen treated and the products obtained, if they are not used immediately after their production, washed with water and dried at a temperature of 20 to 30 "C. 2. Diethylaminohydroxypropyl celluloses. obtainable according to claim I.