DE1011869B - Process for upgrading cellulose or cellulose derivatives - Google Patents

Description

GERMAN

It has been found that natural or regenerated cellulose, cellulose esters or ethers, the still contain free hydroxyl groups, with substituted carbodiimides already at room temperature Isourea ethers can implement if the reaction in the presence of catalytic amounts of Makes copper salts.

The reaction is preferably carried out in such a way that the two components are combined in a homogeneous or heterogeneous phase; and the catalyst is added. In the case of native or regenerated celluloses, it is best to impregnate them beforehand with the copper compound and then allow the carbodiimide to act. For the addition of catalyst, amounts of ¹ Z ₁₀ to V ₁₀₀₀ mol per 1 mol of carbodiimide are sufficient. In most cases the reaction takes place even at normal temperature. The reaction can be accelerated by heating the reaction mixture. The reaction can be carried out in the absence or in the presence of an inert solvent or diluent.

There are all natural celluloses, z. B. Baumr wool, cotton linters or cellulose, and all regenerated celluloses, e.g. B. from viscose or copper oxide ammonia solution regenerated cellulose, in question. The celluloses can be in solution, as fibers, threads, Thread or fabric. - ■;

As cellulose derivatives, all cellulose esters and ethers, such as nitrocellulose, cellulose acetate and methyl cellulose, if they still have free hydroxyl groups, come into question, -y-

For the implementation z. B. the following substituted carbodiimides in question: diisopropylcarbodiimide, n-butyl-cyclohexyl-carbodiimide, dicyclohexylcarbodiimide, methyl tert. butyl-carbodiimide, tert. Butyl-cyclohexyl-carbodiimide, cyclohexyl-phenyl-carbodiimide, tert. Butyl-phenyl-earbodiimide and diphenylcarbodiimide. ■. - ■ - "- ',

From such .GeHulose esters reacted with carbodiimides Shaped structures produced or produced using ethers can easily be colored with acidic dyes. The fastness properties of the dyeings obtained in this way are good. "■ '· -

Also those reacted naturally with carbodiimides or regenerated celluloses can be stained with acidic dyes. Through suitable Choosing the substituents of the carbodiimides, further washing and solvent-resistant effects can be achieved, e.g. Hydrophobization, reduction of the degree of swelling or / and softening, achieve in the celluloses.

It is known to implement substituted carbodiimides with cellulose or cellulose derivatives. For example it has been proposed to use textiles of all kinds ~ with processes for the refinement of cellulose or cellulose derivatives

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Erich Schmidt, Munich, Dr. Fritz Moosmüller

and Dr. Robert Schnegg, Dormagen,

have been named as inventors

treat mono- or disubstituted carbodiimides, the at least one higher alkyl radical in the molecule contain more than 10 carbon atoms. However, the carbodiimide does not settle here the textiles. The dyeability of the same, with acidic dyes is not improved by the process.

It is also known to form alkali cellulose to implement isourea ethers of cellulose with carbodiimide. These reaction products are in aqueous Alkali-soluble, while according to the invention water-insoluble products are obtained with acidic dyes are easy to dye.

. Example 1...

0.5 g of anhydrous copper (II) chloride and 10 g of diisopropylcarbodiimide are dissolved in 200 ecm of acetone. Then 40 g of cotton are added. The liquid is completely absorbed by the fiber. After standing at room temperature for 27 days, the linters are squeezed out and kept for 24 hours Acetone extracted. They then have a nitrogen content of 0.23% (corresponding to 1.03% diisopropyl carbodumid). The linters treated in this way can be easily dyed with acidic dyes. Do you solve the lin? ters in copper oxide ammonia solution, it falls into water, removes copper from the precipitate with 2-n-sulfur acid and washes it with distilled water, the regenerated cellulose is almost unchanged Nitrogen content can also be easily dyed with acidic dyes.

B e i s ρ i e 1 2

270 g linters are mixed with 360 g dope propylcarbo; · dümid, 1 1 carbon tetrachloride and 5 g copper (I), -

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chloride with constant stirring for 72 hours at 80 ° ~ heated. The linters are "pressed off, extracted with acetone in a Soxhlet for 3 hours and then dried at 70 °.

. «" These linters reacted with 'CarboffiimiS "are -""-" dissolved in copper oxide ammonia solution and spun into copper rayon using the bekanatom method. The' copper rayon contains .0.20 to 0.30% nitrogen and leaves "stain well with acidic dyes. '"? /: ..- ■■■ - .. ■■ · _r

give ·. · "With constant stirring, the reaction mixture is refluxed for 8 hours After 3 hours of extraction with acetone, the rayon contains about 2% nitrogen and can be acidic Stain dyes well.

Example8

Artificial silk strands are immersed in 10% aqueous copper acetate solution for 20 minutes at room temperature, spun off and dried at 70 °. Artificial silk strands treated in this way are placed in diisopropylcarbodiimide (liquor ratio 1:20) and heated to about 100 ° for 6 hours. After 3 hours • sets, abgeq "etscht _r 4ibei · -Nacht -in -trockenes- Eyridi * --- E ^ this rayon raktie-n-with-A-cetsn-containing 0.5 / given cent, squeezed, the The remainder of the pyridine is in Va- 15 nitrogen and can be ^{dampened very quickly with acidic dyes at 50 to 60 Q} , the linters can be stained again in good quality,
given anhydrous pyridine and again in vacuo
dried. 2 g of such linkers included with pyridine become ter-t; -butylphenyl-carbodiimide with 8 g
and 100 mg of copper (I) chloride for 48 hours in one

Example 3.:; Cotton linters are '2 hours' in water

Example 9

sealed bottle aui. 80 ° heated. After decopping with 6% sulfuric acid and 3 hours of extraction with methanol - in the Soxhlet. the Lin teYs "0.73% N and are easily dyed with acidic dyes". · "'■" - ■'".'·■"■' · '"· -" - · ■' ■■■

"-._. JBe.LSi.piel 4. .. _.

0.5 g copper® chloride are dissolved in 10 ecm pyridine, and the solution is then diluted with 990 cm water. Pulp is impregnated with this solution and ^: dried at 70 °. 10 g of such pulp impregnated with copper (I) chlorine are mixed with 10 g of methyl tert. butyl-carbodiimide and 150 ecm benzene heated under reflux for 12 hours. After pressing, decoppering with 6% sulfuric acid, every hour: extraction with benzene and drying at -70? .- you get a pulp that dissolves in copper oxide ammonia solution and is then spun into copper rayon or cellulose wool using known methods Regenerated celluloses obtained in this way contain about 0.3% nitrogen and can be easily stained with acidic dyes.

- 907 g cellulose acetate with eiheni acetic acid content voa 55.4% are completely dissolved in 4.5 kg of acetone and mixed with 93 g of methyl tert. butylcärbodiimid added. ^; After thorough mixing, 0.2 g cuprous chloride is added. The solution is used to terminate the reaction ^; Stirred for 5 minutes at about 30 °. After this time, the carbodiimide is converted. The nitrogenous cellulose acetate <N _: content 2.2%) obtained from the solution by precipitation can be stained with acidic dyes.

; -._ _; Example 10

^; In. 180 g of 20% strength acetone cellulose acetate solution (54.2% acetic acid content) are 18.45 g of methyl tert. butyl-carbodiimide and 0.01 g in a vacuum desiccator at 50 ° dehydrated Cu Cl ₂ stirred. The reaction mixture is placed in a closed bottle in a thermostat at 50 ° for 48 hours. Then foils are drawn from it. After extraction for 2 hours with petroleum ether, these have a nitrogen content of 2.23 ⁰ zo.

Example 11

In 50 g of 20% cellulose acetate solution in acetone

4g; Cotton linters, with 0.1 g of copper (I) - 45 (acetic acid content 54.2%) are 6.63 g of tert. Butyl

phenyl carbodiimide and 0.01 g Cu ₂ Cl ₂ stirred in. After 10 days of storage at room temperature, a cellulose acetate is obtained by precipitation of the reaction mixture, which after 2 hours of extract

Chloride and 10 ecm carbon tetrachloride for -20 minutes. After adding -10 ecm of diisopropylcarbodiimide, the reaction mixture is heated under reflux for 8 hours with constant stirring. After 3 hours of extraction in a Soxhlet with acetone, the linters contain 0.96% -N "un # can" be mixed with acidic dyes ^: good coloring "The linters are soluble in copper oxide ammonia solution and can be spun from it using known processes.

■ -: - Example 6 -

- '[ To' 4g cell wool vvgfdeh 50 mg copper (I) chloride and 20 ecm tetrachloride added and stirred for 5 minutes. 5 ecm of diphenyl ¹ carbodiimide are added * "and the reaction mixture is refluxed for 6 hours. After 3 hours of extraction in a Soxhlet with acetone, the reaction product contains about O> ^% nitrogen and Dyes can be dyed and in copper oxide ammonia

55

• solution soluble.

Example 7

4 g rayon are stirred ra ~ \ i 0.1 g of copper (I) chloride tind'lOccmiT ^ trachlÖTkolilenstoff'SMinuten.

65 tion with petroleum ether in the Soxhlet contains 0.8% nitrogen, ■ '-

. . '. : Example 12

In 50 g of 20% cellulose acetate solution in acetone (Acetic acid content 54.2%) are 3.09 g of diisopropylcarbodiimide and 0.01g copper acetate, dissolved in ecm Pyridine, stirred in. After 14 days, the reaction mixture becomes precipitated in distilled water. The fibrous precipitate is filtered off, dried at 70 °, Extracted with petroleum ether in a Soxhlet for 2 hours and then contains 0.74% nitrogen.

For example; i3 .., · ■ '.

_{4.80 g of diisopropylamide and 0.01 g of Cu 2 Cl 3 are} introduced into 50 g of 20% strength acetone cellulose acetate solution (acetic acid content 54.2%). The reaction mixture is refluxed for 6 hours. The reaction product is precipitated in water; away-

© ahn are- ίθ-ccm ' ^: © 1isöpropylearbodiimid zzüge- 70 "sucked, dried at -60 °, in the Soxhlet for 2 hours

1 Oil

Petroleum ether extracted and then contains 0.50% nitrogen.

Example 14

A 10 g strand of desized acetate silk is placed in a solution of 10 cm _{pyridine saturated with Cu 2} Cl ₂ and 99 ° cm water at 20 ° for 20 minutes, squeezed off and dried at 50 °. The strand is then placed in a solution of 25 ecm diisopropylcarbodiimide in 75 ecm petroleum ether at room temperature for 8 days, squeezed off, air-dried and extracted with benzene in a Soxhlet for 2 hours. Acetate silk treated in this way contains 0.3%> nitrogen and can be easily dyed with acidic dyes.

Example 15

_{A 10 g strand of acetate silk prepared with Cu 2} Cl ₂ as in Example 14 is placed in 60 ecm diisopropylcarbodiimide for 8 days, squeezed off, air-dried and extracted with benzene in a Soxhlet for 2 hours. Acetate silk treated in this way contains 1% nitrogen and can be easily dyed with acidic dyes.

If the reaction is carried out at 100 ° instead of at room temperature, the acetate silk contains 1.36% after 2 hours
2.32% nitrogen.

Nitrogen and after 8 hours

Example 16

A solution of 10 g of alcohol-free collodion wool in 50 to 100 ecm of acetone is made after adding 1.8 g Diisopropylcarbodiimide and 0.1 g of copper (I) chloride were stirred for about 4 hours. After 24 hours the Collodion wool was precipitated from its solution with water and washed. You can use acidic wool dyes to be colored.

Claims (2)

PATENT CLAIMS: 1. Process for upgrading cellulose or cellulose derivatives by reacting them with substituted ones Carbodiimides, characterized in that the reaction in the presence of catalytic Quantities of copper salts is made. 2. The method according to claim 1, characterized in that the copper salt is copper (I) chloride is used. Considered publications:
U.S. Patent No. 2,415,043;
British Patent No. 511 536. 1 709 '587/420 7.57