Wrinkle recovery finishing on cotton by using cyclodextrin (phd report)

ABSTRACT BILGEN, MUSTAFA. Wrinkle Recovery for Cellulosic Fabric by Means of Ionic Crosslinking. (Under the direction of Peter Hauser and Brent Smith.) When treated with formaldehyde-based crosslinkers, cellulosic fabrics show improved mechanical stability, wrinkle recovery angles and durable press performance, but N-methylol treatment also causes fabrics to lose strength and later to release formaldehyde, a known human carcinogen. We have discovered that ionic crosslinks can stabilize cellulose using high or low molecular weight ionic materials which do not release hazardous reactive chemicals, but at the same time provide improved wrinkle recovery angles as well as complete strength retention in treated goods. We have varied polyelectrolyte, the ionic content of fabrics, and various features of the application procedure to optimize the results and to develop an in-depth fundamental physical and chemical understanding of the stabilization mechanism. WRINKLE RECOVERY FOR CELLULOSIC FABRIC BY MEANS OF IONIC CROSSLINKING by MUSTAFA BILGEN A thesis submitted to the Graduate Faculty of North Carolina State University in partial fulfillment of the requirements for the Degree of Master of Science TEXTILE CHEMISTRY Raleigh 2005 APPROVED BY: Dr. Peter Hauser (Chair) Dr. Brent Smith (Co-Chair) Dr. Charles Boss (Minor) ii DEDICATION This thesis is dedicated to my family and my wife, Nicole, who supported me with constant love and caring and inspired my interest in studying textile chemistry. iii BIOGRAPHY Mustafa Bilgen was born in December 1, 1978 in Erdemli, Turkey. He graduated from Erzurum Science High School in June 1995. He received the Bachelor of Science degree in Textile Engineering from Department of Engineering and Architecture, Uludag University, Bursa, Turkey in July 1999. After he graduated he worked as a dyeing and finishing supervisor in Akay Textile Dyeing & Finishing Company for one year before he started to help his father for taking care of the family business. He came to North Carolina State University in January 2004, to continue his education and started his master program in Textile Chemistry under the direction of Dr. Brent Smith and Dr. Peter Hauser. iv ACKNOWLEDGEMENTS I would like to thank to the National Textile Center and North Carolina State University for their financial support. I also would like to thank to my advisors, Dr. Hauser and Dr. Smith, for their crucial help and patience during my research and preparation of my thesis. v LIST OF CONTENTS LIST OF TABLES viii LIST OF FIGURES x 1. INTRODUCTION 1 2. LITERATURE REVIEW 3 2.1 Cellulose chemistry 3 2.2 Cellulosic fabric’s nature of wrinkling 5 2.3 Durable Press finishing of cotton 6 2.3.1 Urea-Formaldehyde derivatives 7 2.3.2 Melamine-Formaldyhe derivatives 7 2.3.3 Methylol derivatives of cyclic ureas 8 2.3.4 Effects of formaldehyde based DP finishes on cellulose 9 2.4 Recent developments in non-formaldehyde DP applications 10 2.5 Ionic crosslinking 14 2.6 Preparation of quaternized polymers 16 2.6.1 Chitosan and its reaction with CHTAC 16 2.6.2 Reaction of Cellulose with CHTAC 18 2.7 Carboxymethylation of cellulose 20 2.8 Proposed Research 21 3. EXPERIMENTAL PROCEDURES 23 3.1 Test Materials 23 3.2 Equipments 25 3.3 Application procedures 25 3.3.1 Pad dry cure 25 3.3.2 Pad batch 26 3.3.3 Exhaustion 26 3.4 Analysis and physical property tests 26 3.4.1 Nitrogen analysis 27 3.4.2 FT-IR analysis 27 3.4.3 1 H- NMR analysis 27 3.4.4 Wrinkle recovery angles 28 3.4.5 Tensile strength 28 3.4.6 Whiteness index 28 3.4.7 Stiffness 28 3.5 Reaction of cellulose with chloroacetic acid 29 3.6 Reaction of Cellulose with CHTAC 32 3.7 Synthesis of compounds 35 3.7.1 Molecular weight determination of chitosan 35 3.7.2 Depolymerization of chitosan and characterization 37 3.7.3 Reaction of chitosan with CHTAC 39 3.7.4 Reaction of glycerin and ethylene glycol with CHTAC 51 vi 3.7.5 Reaction of cellobiose and dextrose with CHTAC 53 3.8 Preparation of fabric samples 53 3.9 Crosslinking of carboxymethylated cellulosic fabric 54 3.9.1 Treatment with cationic chitosan 54 3.9.2 Treatment with cationic glycerin 54 3.9.3 Treatment with cationic cellobiose, cationic dextrose and cationic ethylene glycol 55 3.9.4 Treatment with calcium chloride and magnesium chloride 55 3.10 Crosslinking of cationic cellulosic fabric 57 3.10.1 Treatment with PCA and BTCA 57 3.10.2 Treatment with EDTA, NTA and HEDTA 59 3.10.3 Treatment with oxalic acid, citric acid and malic acid 59 4. RESULTS & OBSERVATIONS AND DISCUSSION 60 4.1 Wrinkle recovery angles of conventional durable press finished fabrics 60 4.2 Wrinkle recovery angles of polycation treated anionic cellulosic fabrics 60 4.2.1 Wrinkle recovery angles of cationic chitosan treated fabrics 60 4.2.2 Application of paired t-test analysis on cationic chitosan treatments 68 4.2.3 Wrinkle recovery angles of cationic glycerin treatments 71 4.2.4 Wrinkle recovery angles of cationic cellobiose and cationic dextrose treated fabrics 76 4.2.5 Wrinkle recovery angles of calcium chloride and magnesium chloride treated fabrics 76 4.2.6 Discussion of wrinkle recovery angles for polycation treatments 79 4.3 Wrinkle recovery angles of polyanion treated cationic cellulosic fabrics 82 4.3.1 Wrinkle recovery angles of PCA and BTCA treated fabrics 82 4.3.2 Wrinkle recovery angles of EDTA, NTA and HEDTA treated fabrics 87 4.3.3 Wrinkle recovery angles of oxalic acid, citric acid and malic acid treatments 89 4.3.4 Discussion of wrinkle recovery angles for polyanion treatments 90 4.4 Strength data 92 4.4.1 Tensile strength of conventional durable press finished fabric 92 4.4.2 Strength data of polycation treated anionic cellulosic fabrics 93 4.4.3 Strength data of polyanion treated cationic cellulosic fabrics 96 4.4.4 Discussion of strength data of untreated and treated fabrics 98 4.5 CIE whiteness index data 101 4.5.1 CIE whiteness index of conventional durable press treated fabric 101 4.5.2 CIE whiteness index of polycation treated anionic cellulosic fabrics 102 4.5.3 CIE whiteness index of polyanion treated cationic cellulosic fabrics 104 4.5.4 Discussion of whiteness index of untreated and treated fabrics 106 4.6 Stiffness data 108 4.6.1 Stiffness of conventional durable press treated fabrics 109 4.6.2 Stiffness data of polycation treated anionic cellulosic fabrics 109 4.6.3 Stiffness data of polyanion treated cationic cellulosic fabrics 111 4.6.4 Discussion of stiffness data of untreated and treated fabrics 113 vii 5. CONCLUSIONS 116 6. RECOMMENDATIONS FOR FUTURE WORK 118 7. LIST OF REFERENCES 121 8. APPENDIX 126 8.1 Wrinkle recovery angles 126 8.2 Breaking strength 133 8.3 CIE whiteness index 137 8.4 Stiffness 141 8.5 Nitrogen analysis 145 viii LIST OF TABLES Table 3.2 Results for carboxymethylation of cellulosic fabrics 32 Table 3.3 Scheme of intrinsic viscosity measurement for the low viscosity chitosan 36 Table 3.4 Properties of the Low Viscosity chitosan 37 Table 3.5 The intrinsic viscosity and M v of depolymerized chitosans 39 Table 4.1 Paired t-test results for dry wrinkle recovery angles of cationic chitosan treated fabrics 69 Table 4.2 Paired t-test results for wet wrinkle recovery angles of cationic chitosan treated fabrics 70 Table 4.3 Paired t-test results for dry/wet wrinkle recovery angles of Ca ++ and Mg ++ treated fabrics 79 Table 4.4 Paired t-test results for dry/wet wrinkle recovery angles of PCA and BTCA treated fabrics 87 Table A.1 Dry and wet wrinkle recovery angles for molecular weight of 3.2 x 10 4 g/mole cationic chitosan treated fabrics 126 Table A.2 Dry and wet wrinkle recovery angles for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics 127 Table A.3 Dry and wet wrinkle recovery angles for molecular weight of 6.11 x 10 5 g/mole cationic chitosan treated fabrics 127 Table A.4 Dry and wet wrinkle recovery angles for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics by exhaustion method 128 Table A.5 Dry and wet wrinkle recovery angles for cationic glycerin treated fabrics 128 Table A.6 Dry and wet wrinkle recovery angles for cationic glycerin treated fabrics by exhaustion method 129 Table A.7 Dry and wet wrinkle recovery angles for cationic cellobiose and cationic dextrose treated fabrics 129 Table A.8 Dry and wet wrinkle recovery angles for calcium chloride and magnesium chloride treated fabrics 130 Table A.9 Dry and wet wrinkle recovery angles for PCA treated fabrics 130 Table A.10 Dry and wet wrinkle recovery angles for BTCA treated fabrics 131 Table A.11 Dry and wet wrinkle recovery angles for EDTA treated fabrics 131 Table A.12 Dry and wet wrinkle recovery angles for NTA treated fabrics 132 Table A.13 Dry and wet wrinkle recovery angles for HEDTA treated fabrics 132 Table A.14 Dry and wet wrinkle recovery angles for oxalic, malic and citric acid treated fabrics 133 Table A.15 Breaking strength data for molecular weight of 3.2 x 10 4 g/mole cationic chitosan treated fabrics 134 Table A.16 Breaking strength data for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics 134 ix Table A.17 Breaking strength data for molecular weight of 6.11 x 10 5 g/mole cationic chitosan treated fabrics 135 Table A.18 Breaking strength data for cationic glycerin treated fabrics 135 Table A.19 Breaking strength data for calcium chloride and magnesium chloride treated fabrics 136 Table A.20 Breaking strength data for PCA treated fabrics 136 Table A.21 Breaking strength data for BTCA treated fabrics 137 Table A.22 Whiteness index data for molecular weight of 3.2 x 10 4 g/mole cationic chitosan treated fabrics 138 Table A.23 Whiteness index data for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics 138 Table A.24 Whiteness index data for molecular weight of 6.11 x 10 5 g/mole cationic chitosan treated fabrics 139 Table A.25 Whiteness index data for CG treated fabrics 139 Table A.26 Whiteness index data for calcium and magnesium chloride treated fabrics -140 Table A.27 Whiteness index data for PCA treated fabrics 140 Table A.28 Whiteness index data for BTCA treated fabrics 141 Table A.29 Stiffness data for molecular weight of 3.2 x 10 4 g/mole cationic chitosan treated fabrics 142 Table A.30 Stiffness data for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics 142 Table A.31 Stiffness data for molecular weight of 6.11 x 10 5 g/mole cationic chitosan treated fabrics 143 Table A.32 Stiffness data for cationic glycerin treated fabrics 143 Table A.33 Stiffness data for calcium chloride and magnesium chloride treated fabrics 144 Table A.34 Stiffness data for PCA treated fabrics 144 Table A.35 Stiffness data for BTCA treated fabrics 145 Table A.36 Nitrogen analysis data for molecular weight of 3.2 x 10 4 g/mole cationic chitosan treated fabrics 146 Table A.37 Nitrogen analysis data for molecular weight of 1.4 x 10 5 g/mole cationic chitosan treated fabrics 146 Table A.38 Nitrogen analysis data for molecular weight of 6.11 x 10 4 g/mole cationic chitosan treated fabrics 147 Table A.39 Nitrogen analysis data for cationic glycerin treated fabrics 147 [...]... weight of chitosan and concentration on dry wrinkle recovery angles of cationic chitosan treated fabrics - 67 Figure 4.6 Effect of molecular weight of chitosan and concentration on wet wrinkle recovery angles of cationic chitosan treated fabrics - 67 Figure 4.7 Effect of carboxyl content and concentration on dry wrinkle recovery angles of cationic glycerin treated... evaluated as non-formaldehyde durable press finish to produce wrinkle- resistance and antimicrobial properties for cotton fabrics [30] The carboxylic groups in the chitosan citrate structure were used as active sites for its fixation onto cotton fabrics The fixation of the chitosan citrate on the cotton fabric was done by the padding of chitosan citrate solution onto cotton fabrics followed by a dry -... Effect of carboxyl content and concentration on wet wrinkle recovery angles of cationic glycerin treated fabrics 72 Figure 4.9 Effect of carboxyl content and concentration on %Nitrogen content of cationic glycerin treated fabrics - 74 Figure 4.10 The relationship between %Nitrogen content of the fabrics and dry/wet wrinkle recovery angles... Effect of carboxyl content and concentration on wet wrinkle recovery angles of cationic chitosan treated fabrics 62 Figure 4.3 Effect of carboxyl content and concentration on %Nitrogen content of cationic chitosan treated fabrics 64 Figure 4.4 The relationship between %Nitrogen content of the fabrics and dry/wet wrinkle recovery angles... fixed and concentration on dry wrinkle recovery angles of EDTA treated fabrics - 88 Figure 4.18 Effect of %Nitrogen fixed and concentration on wet wrinkle recovery angles of EDTA treated fabrics - 89 Figure 4.19 Effect of treatment on dry wrinkle recovery angles - 91 Figure 4.20 Effect of treatment on wet wrinkle recovery. .. 4.14 Effect of %Nitrogen fixed and concentration on wet wrinkle recovery angles of PCA treated fabrics - 84 Figure 4.15 Effect of %Nitrogen fixed and concentration on dry wrinkle recovery angles of BTCA treated fabrics - 85 Figure 4.16 Effect of% Nitrogen fixed and concentration on wet wrinkle recovery angles of BTCA treated fabrics... Figure 4.21 Effect of carboxyl content and concentration on breaking strength of the cationic chitosan (molecular weight of 1.4 x 105g/mole) treated fabrics 94 Figure 4.22 Effect of carboxyl content and concentration on breaking strength of the cationic glycerin treated fabrics 95 Figure 4.23 Effect of carboxyl content and concentration on breaking strength of the... x Figure 4.11 Effect of carboxyl content on dry wrinkle recovery angles of calcium and magnesium treated fabrics - 77 Figure 4.12 Effect of carboxyl content on wet wrinkle recovery angles of calcium and magnesium treated fabrics - 78 Figure 4.13 Effect of %Nitrogen fixed and concentration on dry wrinkle recovery angles of PCA treated fabrics... followed by a treatment with a polycation, such as, cationized chitosan, cationized glycerine, cationized ethylene glycol, cationized dextrose or cationized D-celobiose We also observed WRA improvements with divalent cations such as Ca++ and Mg++ Method 2 consists of the reaction of cellulose with CHTAC to produce cationic cellulose, followed by the application of polyanion, such as, polycarboxylic acids... concentration on whiteness index of the BTCA treated fabrics 106 Figure 4.34 Effect of treatment on whiteness index 108 Figure 4.35 Effect of carboxyl content and concentration on stiffness of the cationic chitosan (molecular weight of 1.4 x 105g/mole) treated fabrics -110 Figure 4.36 Effect of carboxyl content and concentration . carboxyl content and concentration on wet wrinkle recovery angles of cationic chitosan treated fabrics 62 Figure 4.3 Effect of carboxyl content and concentration on %Nitrogen content of cationic. of carboxyl content and concentration on dry wrinkle recovery angles of cationic glycerin treated fabrics 72 Figure 4.8 Effect of carboxyl content and concentration on wet wrinkle recovery angles. OBSERVATIONS AND DISCUSSION 60 4.1 Wrinkle recovery angles of conventional durable press finished fabrics 60 4.2 Wrinkle recovery angles of polycation treated anionic cellulosic fabrics 60 4.2.1 Wrinkle