2009.11.27 Synthesis of a phthalimide-based alkali-clearable azo disperse dye and analysis of its alkali-hydrolysis kinetics Minyoung Eom Advisor: Prof. Joonseok Koh Department of Textile Engineering The Graduate School of Konkuk University

Contents Introduction Experimental Results & Discussion Conclusions

Introduction Dyesolid Dyemicelles Dyedissolved Dyefiber Disperse Dyeing Mechanism Dyesolid Dyemicelles Dyedissolved Dyefiber Dye Dispersing agent POLYESTER

Introduction Reduction Clearing(R/C) of dyed Polyester R/C Before R/C Penetrated dyes Non-penetrated dyes Laundering Low Fastness Staining R/C 80oC, 20min After R/C Wash off Laundering Fastness improvement No staining

“high BOD and pH values” Introduction Reduction Clearing(R/C) of azo disperse dye “Carcinogenic” “high BOD and pH values” Colorless / No substantivity for PET - R/C conditions : 80℃, 20min ( Na2S2O4 2g/L + NaOH 2g/L ) Environmental problem Alkali-clearable disperse dye Solution ?

Introduction Alkali-clearable disperse dyes 1. Diesters 2. Thiophenes Water-insoluble Substantivity for PET Water-soluble No substantivity for PET 1. Diesters Dispersol PC (ICI,1976) Water-insoluble Substantivity for PET Colorless Decomposition Product 2. Thiophenes Dispersol PC (ICI,1977)

No substantivity for PET Introduction Alkali-clearable disperse dyes Water-insoluble Substantivity for PET Water-soluble No substantivity for PET 3. Phthalimides Dyes and Pigments (J. Koh,1998) Water-insoluble Affinity for PET Water-soluble No affinity for PET 4. Fluorosulfones Dyes and Pigments (J. Koh,2000)

(a) reduction clearing Introduction Previous study < UV-Visible spectra of dye at reduction clearing(a) and alkali clearing(b) condition. > (a) reduction clearing (b) alkali clearing < I.R. spectrum of alkali-hydrolyzed dye. > < Mass spectrum of alkali-hydrolyzed dye (X1, X2 = H, Na). > * J. S. Koh, J. P. Kim, J. Soc, Dyers. Colour., 114(4), 121, 1998 * J. S. Koh, J. P. Kim, Dyes and Pigments, 37(3), 265, 1998

Introduction Objectives Phthalimide-based alkali-clearable azo disperse dye and its hydrolyzed form were synthesized in order to investigate the hydrolysis kinetics. Hydrolysis kinetics of the synthesized dye at various conditions was investigated by using a HPLC to assess their feasibility of the alternative clearing process in polyester dyeing.

Experimental Dye synthesis Synthesis of dye intermediates Nitration Alkylation Amination Diazotization and Coupling reaction Diazotization Coupling

Experimental Hydrolyzed dye synthesis Diazotization and Coupling reaction Diazotization Coupling

Experimental Alkali-hydrolysis analysis Determination of optimum dyeing pH Procedure 20min 30℃ 130℃ Dilution with same amount of acetonitrile Immediate Cooling Sample preparation for HPLC (ACN:Water = 80:20) HPLC anlaysis 2.0℃/min ‘Blank dyeing’ 1 wt% Dye stock solution Buffer solution (pH 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0)

Experimental Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures 40min 70/80/90/100℃ 5 10 15 20 25 30 35 40 (min) Hydrolysis analysis pH buffer solution (pH 8.0, 9.0, 10.0, 11.0, 12.0) 1 wt% Dye stock solution Temp. : 70, 80, 90, 100oC withdrawing at 5min intervals for 40min Thermostatted oil bath Procedure Sampling from dye solution at 5min intervals Immediate neutralizing to pH 5.0-6.0 (with dilute HCl followed by Cooling) Sample preparation for HPLC(ACN:Water=80:20) HPLC anlaysis A

Results and Discussion Characterization of synthesized Intermediates and Dyes a b c d Intermediates 1) 4-nitrophthalimide d NH NO2 asym sym FT-IR a b c 1H-NMR

Results and Discussion Characterization of synthesized Intermediates and Dyes a b c d Intermediates 2) 4-nitro-N-methylphthalimide C-H C-N FT-IR a b c d 1H-NMR

Results and Discussion Characterization of synthesized Intermediates and Dyes a b c d e Intermediates 3) 4-amino-N-methylphthalimide FT-IR NH asym sym NH2 1H-NMR a b c d e

Results and Discussion Characterization of synthesized Intermediates and Dyes a b c d e f g h HPLC (Purity) 99.87 % Spectral properties λmax : 489 nm (in DMF) εmax : 34,108 lmol-1cm-1 (in DMF) m.p.  187.3 oC Dye-1 FT-IR C-N 1H-NMR a b c d h e~g

Results and Discussion Characterization of synthesized Intermediates and Dyes a b c d e f g h HPLC (Purity)  99.60 % Spectral properties λmax : 445 nm (in DMF) εmax : 38,196 lmol-1cm-1 (in DMF) m.p.  189.5 oC Dye-2 (Hydrolyzed form) FT-IR C-N C=O OH 1H-NMR a b c d~g h

Results and Discussion Alkali-hydrolysis analysis Determination of optimum dyeing pH Blank dyeing Polyester dyeing < Stability of Dye at various pHs > < Color strength(K/S) of dyed polyester fabrics at various pHs >

Results and Discussion Treatment : 20min at 80oC R/C - Na2S2O4 2g/L + NaOH 2g/L A/C (1) - NaOH 2g/L A/C (2) - Na2CO3 20g/L, 10g/L, 5g/L HPLC analysis  ACN : Water = 80:20, at 449nm Alkali-hydrolysis analysis Determination of optimum clearing conditions Parent dye (RT: 5.5min) p H (RT: 1.1min) Synthesized hydrolyzed dye Reference peaks Hot Rinse p H Reduction Clearing (Na2S2O4 2g/L + NaOH 2g/L) H

Results and Discussion Alkali-hydrolysis analysis Treatment : 20min at 80oC HPLC analysis  ACN : Water = 80:20, at 449nm Determination of optimum clearing conditions H Alkali Clearing (NaOH 2g/L) (Na2CO3 20g/L) (Na2CO3 10g/L) (Na2CO3 5g/L) The synthesized dye is expected to be washed off at mild alkaline condition.

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures < Hydrolysis behavior of Dye in buffers of various pHs at 70oC > pH 8 pH 9 pH 10 pH 11 pH 12 ● Parent dye Hydrolyzed dye ━ Regression

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures < Hydrolysis behavior of Dye in buffers of various pHs at 80oC > pH 8 pH 9 pH 10 pH 11 pH 12 ● Parent dye Hydrolyzed dye ━ Regression

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures < Hydrolysis behavior of Dye in buffers of various pHs at 90oC > pH 8 pH 9 pH 10 pH 11 pH 12 ● Parent dye Hydrolyzed dye ━ Regression

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures < Hydrolysis behavior of Dye in buffers of various pHs at 100oC > pH 8 pH 9 pH 10 ● Parent dye Hydrolyzed dye ━ Regression

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures 90oC 100oC 80oC 70oC

Results and Discussion Alkali-hydrolysis analysis Hydrolysis behavior at various pHs and temperatures < Residues of parent dye vs time of hydrolysis t at various pHs and temperatures > pH 8 pH 9 pH 11 pH 12 70 oC 80 oC 90 oC 100 oC pH 10

Pseudofirst-order rate law Results and Discussion Alkali-hydrolysis analysis P + OH- H Alkali-hydrolysis Pseudofirst-order rate law Integrated rate law

Results and Discussion Alkali-hydrolysis kinetics Hydrolysis behavior at various pHs and temperatures < Plot of ln(A0/A) vs time of hydrolysis t at various temperatures > ln(A0/A) = kps1t pH 8 pH 9 pH 10 pH 11 pH 12

Results and Discussion Alkali-hydrolysis kinetics Hydrolysis behavior at various pHs and temperatures ln(A0/A) = kps1t < Correlation coefficients (r) in the linear regression and pseudofirst-order hydrolysis rate constants at different pHs and temperatures > 70oC 80oC 90oC 100oC kps1 r pH 8.0 0.000087 N/A 0.0030 0.976 0.0130 0.984 0.0303 0.975 pH 9.0 0.0035 0.0153 0.993 0.0356 0.998 0.5361 0.992 pH 10.0 0.0096 0.997 0.0634 0.989 0.2653 pH 11.0 0.1319 0.2441 0.6105 0.963 pH 12.0 0.2366 0.999 0.4293 0.6646 0.948

Perspiration (Staining) Results and Discussion Fastness properties * R/C (Reduction Clearing) : Na2S2O4 2g/L + NaOH 2g/L * A/C (Alkali Clearing) : Na2CO3 1g/L Wash fastness (ISO 105-C06 A2S) Conditions Staining Change Dyeing Clearing Wool Acryl PET Nylon Cotton Acetate 2%owf R/C 4-5 4 2-3 3-4 A/C 3 Perspiration (ISO 105-E04) / Rubbing (ISO 105 X12) fastness Conditions Perspiration (Staining) Rubbing Dyeing Clearing Wool Acryl PET Nylon Cotton Acetate Dry Wet Alkaline Acid 2%owf R/C 4 4-5 5 A/C

Conclusions Hydrolysis kinetics of a phthalimide-based alkali-clearable azo disperse dye was investigated : The dye was most stable at the pH of less than 4.5 and it was almost completely hydrolyzed at the pH of over 7.0 at dyeing temperature. The alkaline hydrolysis of the synthesized dye in buffered alkaline solution at constant temp. followed pseudofirst-order kinetics. The phthalimide-based azo disperse dye showed an excellent alkali-clearable property under mild alkaline condition, which enables alkaline treatment to substitute for reduction clearing : ex. 98% hydrolyzed at pH 11, 80℃ for 20min

Thank You !