Novel Possibilities in Chemical Pretreatment and Finishing of Cotton Fabrics Dissertation zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften – Dr. rer. nat. – vorgelegt von Vahid Ameri Dehabadi geboren in Kashan/Iran Institut für Deutsches Textilforschungszentrum Nord-West gGmbH der Universität Duisburg-Essen 2012 Die vorliegende Arbeit wurde im Zeitraum von Nov 2008 bis Juli 2012 im Arbeitskreis von Prof. Dr. Gutmann am Institut für Deutsches Textilforschungszentrum Nord-West gGmbH der Universität Duisburg-Essen durchgeführt. Tag der Disputation: 10.12.2012 Gutachter: Prof. Dr. Gutmann Prof. Dr. Ulbricht Vorsitzender: Prof. Dr. Spohr Erklärung Hiermit versichere ich, dass ich die vorliegende Arbeit mit dem Titel „Novel Possibilities in Chemical Pretreatment and Finishing of Cotton Fabrics ” selbst verfasst und keine außer den angegebenen Hilfsmitteln und Quellen benutzt habe, und dass die Arbeit in dieser oder ähnlicher Form noch bei keiner anderen Universität eingereicht wurde. Essen, im Juli 2012 Vahid Ameri Dehabadi Novel Possibilities in Chemical Pretreatment and Finishing of Cotton Fabrics Von der Fakultät für Chemie der Universität Duisburg-Essen zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigte Dissertation von Vahid Ameri Dehabadi Essen–DeutsChland Juli 2012 Acknowledgment I am heartily thankful to my supervisor Prof. Dr. JoChen Stefan Gutmann, whose enCouragement, guidanCe and support from the initial to the final level enabled me to develop an understanding of the subjeCt. I also must deClare my speCially thanks to retired Prof. Dr. ECkhard SChollmeyer, who had kindly helped and let me to Continue my study in University of Duisburg- Essen. I owe my deepest gratitude to Dr. Hans-Jürgen BusChmann and Dr. Klaus Opwis, who without their support, patienCe and guidanCe this study would not have been Completed. I am indebted to many of my Colleagues in Deutsches Textilforschungszentrum Nord-West e. V. to support me during Completion of this projeCt: Dr. Reiner Benken, Dr. Dirk Knittel, Dr. Torsten Textor, Dr. Thomas Mayer-Gall, Harald Fink, Ulrike Artz, Andrea FisCher, Leonie Derksen and Elke Roskothen. And finally, I would like to thank my dear wife, Nazanin, for her understanding and endless love, my family, speCially my mother, who are not by my side but their warm enCouragements from a long distanCe, my home Country, always warm me up to overCome the Challenge in my studies and my dear friends Habib ShalChian, Abbas Aghaei and Kamal Arass. Vahid Ameri Dehabadi To: my love Nazanin, my mother, & my father, whose memory is always with me Page | I Table of Contents List of Figures .................................................................................................... IV List of Tables ................................................................................................... VIII List of Equations ................................................................................................ IX Abstract ............................................................................................................. 1 1 Combination of Acid-Demineralization and Desizing of Cotton Fabrics by Using Acid-Stable Starch-Converting enzymes ............................................... 3 1.1 Introduction .............................................................................................. 4 1.2 State of research ........................................................................................ 6 1.2.1 Structure of cotton ................................................................................................ 6 1.2.2 Desizing of cotton ............................................................................................... 10 1.2.3 Acid demineralization ......................................................................................... 11 1.2.4 Enzymatic processes of textiles ........................................................................... 11 1.2.4.1 StruCture and funCtions of enzymes ........................................................... 11 1.2.4.2 EnzymatiC deComposition of hydrogen peroxide ........................................ 14 1.2.4.3 Biofinishing of CellulosiC fibers by Cellulases ............................................... 16 1.2.4.4 EnzymatiC sCouring of CellulosiC fibers ........................................................ 17 1.2.4.5 EnzymatiC bleaching of CellulosiC fibers ...................................................... 18 1.2.4.6 EnzymatiC finishing of protein fibers ........................................................... 19 1.2.4.7 EnzymatiC treatment of synthetiC fibers ..................................................... 20 1.2.4.8 EnzymatiC desizing of Cotton ....................................................................... 20 1.3 Aims of study ........................................................................................... 25 1.4 Basic approaches ..................................................................................... 26 1.5 Experimental ........................................................................................... 28 1.5.1 Materials ............................................................................................................. 28 1.5.1.1 Enzymes ...................................................................................................... 28 1.5.1.2 Cotton fabriC ............................................................................................... 28 1.5.1.3 Buffer solutions and other ChemiCals .......................................................... 28 1.5.2 Methods .............................................................................................................. 29 1.5.2.1 EnzymatiC desizing of Cotton fabriC ............................................................. 29 1.5.2.2 Evaluation of desizing performanCe ............................................................ 29 1.5.2.3 Measurement of the CationiC metals .......................................................... 30 Page | II 1.6 Results and discussion ............................................................................. 32 1.6.1 Evaluation of enzymatic desizing ........................................................................ 32 1.6.2 Using chelating agents in enzymatic desizing ..................................................... 43 1.6.3 Measurement of the remaining cationic metals ................................................. 51 2 Multifunctional Finishing of Cotton Fabrics Using Carboxylated Polyamines 57 2.1 Introduction ............................................................................................ 58 2.2 State of Research ..................................................................................... 61 2.2.1 Durable press finishing of cotton fabrics ............................................................. 61 2.2.1.1 Formaldehyde-based finishing agents ........................................................ 61 2.2.1.2 Formaldehyde-free finishing agents ........................................................... 64 2.2.1.3 PolyCarboxyliC acids as formaldehyde-free finishing agents ....................... 68 2.2.2 Flame retardant finishing of cotton fabrics ........................................................ 72 2.2.2.1 MeChanisms of flame retardants ................................................................ 72 2.2.2.2 Non-durable and semi-durable flame retardants ....................................... 76 2.2.2.3 Durable flame retardants ............................................................................ 78 2.3 Aim of study ............................................................................................ 83 2.4 Basic approaches ..................................................................................... 84 2.5 Materials and methods ............................................................................ 89 2.5.1 Materials ............................................................................................................. 89 2.5.2 Methods .............................................................................................................. 89 2.5.2.1 Carboxylation of polyvinylamine (PVAm) .................................................... 89 2.5.2.2 ChemiCal CharaCterization of Carboxylated PVAm ...................................... 89 2.5.2.3 Finishing of Cotton with Carboxylated PVAm .............................................. 90 2.5.2.4 GravimetriC test .......................................................................................... 90 2.5.2.5 FTIR spectrosCopy of finished Cotton fabriC ................................................ 91 2.5.2.6 Determination of CarboxyliC groups in finished Cotton with Carboxylated PVAm ........................................................................................................... 91 2.5.2.7 Measurement of free amino groups in treated Cotton ............................... 92 2.5.2.8 Dyeing with reaCtive dyes ........................................................................... 93 2.5.2.9 Measurement of wrinkle reCovery angle, tensile strength, whiteness index and wash fatness ......................................................................................... 93 2.5.2.10 Evaluation of fastness properties of dyed fabriCs ....................................... 93 2.5.2.11 Color measurement of dyed fabriCs ...........................................................