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The direct diazotation of wool was applied with three different diazonium salts (A, B and C).

The experiment conditions were adjusted for forming the azo dyes by coupling. The amino acid analyses of direct diazotation of wool with the three diazonium salts under various conditions are listed in Table 6-4.

Table 6-4: The results of amino acid analysis of direct diazotated wool with diazonium salts A, B and C.

Sample Nr. T

[°C] t [h] pH Colour Reacted Amino Acids [%]*

appearance Tyrosine Histidine Phenyl- alanine

A1 0 2 12 19 3 4

* Percentage is taken to the respective amino-acid

In order to find out whether the direct diazotation can be taken place according to the industry required condition pH= 4−5 and at room temperature, the direct diazotation of wool with diazonium salts A and B have also been done in acidic environment and at room temperature.

The amino acid analysis of the direct diazotation of wool showed clearly that no coupling of

diazonium salt A with amino acids of wool occured in reactions taking place in the acidic environment and within a temperature range of room temperature (Table 6-4). The amino acid tests with diazonium salt B showed that the coupling may take place in the acidic environment and for a temperature range equal to or above room temperature. It showed that diazonium salt B is more reactive and has less steric effect than diazonium salt A; therefore B could better penetrate into the wool and form azo coupling in acidic environment and at room temperature.

The colours that were observed under these conditions are possibly caused by retention of azo compounds, which could be developed by coupling of diazonium salts with each other.

Only the direct diazotation of wool reacted with diazonium salt A at pH 12−13 and 0 °C in an aqueous sodium hydroxide solution resulting in a coupling of amino acids, tyrosine and phenylalanine with diazonium salts, forming azo dyes in the wool. After a reaction time of 120 min of wool in an aqueous sodium hydroxide solution with diazonium A, 19% of phenylalanine and 4% of tyrosine in the wool sample A1 reacted.

A direct diazotation of wool with diazonium salt B at pH 12−13 and 0 °C in an aqueous sodium hydroxide reacted best with the amino acids tyrosine and histidine, coupled with diazonium salts B forming azo dyes. After a reaction time of 180 min of wool in an aqueous sodium hydroxide solution with diazonium B, 12% of tyrosine and 34% of histidine in the wool sample B13 reacted.

An azo coupling of diazonium salt B with amino acids of wool at RT and in an acidic medium is possible. The wool sample B2 was dipped in an aqueous sodium carbonate solution (to reach the pH of 5) for 120 min at 20 °C. It was observed, that 20% of tyrosine, reacted with diazonium salt B. The wool samples soaked in the solution at 20 °C for 24 h showed a high proportion of amino acids reacted with the diazonium salt B, proportion which increases with the pH-value; sample B10 (pH 9) has about 25% histidine reacted, and sample B14 (pH 12) exhibits almost 61% histidine reacted with diazonium B.

The wool samples which were dipped in the solution at 0 °C for 3 h showed a higher proportion of amino acids reacted with the diazonium salt B, proportion which increases with the pH-value; sample B3 (pH 5) has about 25% histidine and 4% phenylalanine reacted.

Sample B11 (pH 9) exhibits 40% histidine reacted with diazonium B and sample B14 (pH 12)

has almost 34 % histidine, 12% tyrosine reacted. The azo coupling yield increases with the reaction time and pH-value. Histidine was mostly diazotised with diazonium salt B.

In the direct diazotation of wool with diazonium C in sodium carbonate solution at pH 11, a lower percentage of diazobenzolsulfonic acid couples with amino acids of the wool. The wool (sample C2) was dipped in aqueous sodium carbonate solution for 120 min, it was observed in sample C2 that 15% phenylalanine and 1% tyrosine reacted with diazonium salt C. This could be due to the fact that soda is not as active as aqueous sodium hydroxide. This assumption is also supported by the fact that a high proportion of amino acids of wool in sample C3 (34%

phenylalanine) reacted with diazonium C in sodium hydroxide at pH 12 −13.

These results are contrary to the previous results of the azo coupling where single (pure) amino acids reacted with diazonium salt C. The results showed that the coupling of Boc-tyrosine and Boc-histidine with diazonium C in sodium carbonate solution reacted best and with phenylalanine had no reaction.

The wool fibres treated with sodium hydroxide solution are severely damaged and the resulted wool fabrics are usually rough. This is in agreement with what literature describes about the dyeing of the wool. This leads to the problem that the most favorable conditions for developing the colour damage the wool so that further processing is impossible.

In general, the resulting colours, despite the small number of reacted amino acids are relative intense. It is also not known what amount of amino acids reacts industrially. It would be interesting to find out the impact of diazonium salts on the aliphatic amino acids of wool. The dyeing tests performed so far, showed that even if no aromatic amino acid reacts with diazonium salt still a rich colour evolves. A possible explanation is that the diazonium compound accumulated in protein. The tests for colour-fastness of the dyed wool are of interest in order to find out whether the colour comes by dimerization of the diazonium compound or by reaction with the protein of wool.

6.4 Conclusions

Generally, an azo coupling with amino acids is possible, but the formation of the products is mainly dependent on pH, the reagents and the reactivity of the diazonium salts.

Investigations of the in situ dye formation by direct diazotation of wool showed that using a small quantity of diazonium salt of A, B or C, respectively, is sufficient enough to couple with the amino acids in wool. Despite the small number of reacted amino acids the resulting colour shades are relatively intense. A high chemical reactivity seems to be the reason for which, regardless of the conditions used in the dyeing tests, the wool dyes. It showed that it could be possible to use diazonium salt of 4-naphthalene-1-sulfonic acid (B) as dye on wool in a commercial wool dyeing procedure under mild conditions (pH= 5, RT).

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Danksagung

Die vorliegende Arbeit wurde auf Anregung und unter der Leitung von Herrn Prof. Dr. Martin Möller am DWI- Leibniz-Institut für Interactive Materialien durchgeführt. Meinem Doktorvater möchte ich für die Breitstellung des Themas, die freundliche Betreuung in fachlichen Fragen, sowie auch der zugekommenen Unterstützung und dem entgegen gebrachtem Vertrauen danken.

Auch Prof. Dr. Alexander Böker danke ich für die freundliche Übernahme des Koreferats.

Mein besonderer Dank gilt Herrn Prof. Dr. Oliver Weichold für seine tatkräftige Betreuung, vielfältigen Anregungen und seine buchstäblich jederzeit vorhandene Diskussions- und Hilfsbereitschaft zu Beginn meiner Promotionszeit.

Herrn Dr. Crisan Popescu möchte ich ganz herzliche danken für die umfassende wissenschaftliche Betreuung sowie seine ständige Diskussions- und Hilfsbereitschaft und die kritische Durchsicht des Manuskripts.

Recht herzlich möchte ich auch Dr. Felix Plamper, Dr. David Skinner und Dr. Smriti Singh für ihre kritische Durchsicht dieser Arbeit und Hilfsbereitschaft.

Des Weiteren möchte ich mich bei meinem Praktikanten Hari Puspitosari, Noah Abraham, Jenny Sass, Maria Guerrero, Xingjun Zhang, Shan-shan Wang, Laura Cegerli und Frederic Peter Sylvain Buttler bedanken, die durch Ihr motiviertes Arbeiten maßgeblich zum Gelingen dieser Arbeit beigesteuert.

Meine Kollegin und meine Freundin, Anna Manova gilt mein herzlicher Dank für ihre stete Hilfsbereitschaft und das nette Arbeitsklima im Labor.

Den Mitarbeitern des DWI, die zum Gelingen dieser Arbeit beigetragen haben, danke ich besonders Herrn Dr. Kim Ho-Phan für die REM-Aufnahmen sowie Frau Angelika Kaiser und Frau Josi Hahn für die Reißfestigkeitsmessungen. Dr. Josef Fohles und Frau Petra Esser danke ich für die Durchführung der Aminosäureanlysen. Herrn Dr. Tilmann gilt mein herzlicher Dank für die Durchführung der IR- und Raman-Messungen.

Weiterhin danke meine Freunden, die zum Gelingen dieser Arbeit beigetragen haben, auch über die Grenzen der RWTH Aachen hinaus. Bei meinem besten und lieben Freund Herr Dr.

biol. hum. Dipl.-Ing. Andrew Boryor möchte ich ganz besonders für seinen Beistand danken.

Ohne seine großartige Unterstützung und ermüdliche Hilfsbereitschaft wäre das Gelingen dieser Arbeit nicht möglich.

Besonderer Dank gebührt meine Eltern für Ihre Vetrauen und die Ermöglichung meiner Ausbildung in Deutschland.

Last but not least gilt mein Dank meinem liebsten Mann, deren seine seelische Unterstützung die Arbeit erst möglich machte.

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