Investigation of Dye-Fiber Reactions in SC-CO2

NSF Green Processing Summer Research Experience for Undergraduates Faculty Mentors: Dr. David Hinks and Dr. Gerardo Montero

Graduate Student Mentor: Mr. Ahmed El-Shafei

North Carolina State University, College of Textiles

Undergraduate Student: Nneka C. Ubaka-Adams

Bennett College and North Carolina Agricultural and Technical State University
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Objectives
To demonstrate and quantify dye-fiber covalent bond formation between selected dyes and nylon, wool and cotton fibers in a supercritical carbon dioxide medium To optimize reaction conditions (temperature, pressure and time) To conduct a literature review

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Background
Conventional dye-fiber reactions use water as a transport medium, and result in:
Low reaction efficiency due to the competing hydrolysis reaction with hydroxyl ions in water (hydrolyzed dye cannot react w/fiber)

Environmental problems due to residual, unreacted/hydrolyzed dye present in effluent

Replacing water with supercritical fluids (SCF) as a

transport medium can result in:

Eliminating toxic waste (no hydrolyzed by-product) Lower costs for the entire dyeing process
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Conventional aqueousbased dye-fiber reaction

Et O H HOOC(CH2)4 C N (CH2)6 H O O H H H O C C S H O N N N Et N C (CH2)4 C N (CH2)6NH2 n

Polyamide (nylon 6.6.)

H2O 100 0C, 2h

Et

O H HOOC(CH2)4 C N (CH2)6

H O

O H

H H O C C S H H O N

N Et

N C (CH2)4 C N (CH2)6N n

+
O HO CH2 CH2 S O N N N Et
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Et

Dye-Fiber Reaction in SC CO2

Et O H HOOC(CH2)4 C N (CH2)6 H O O H H H O C C S H O N N N Et N C (CH2)4 C N (CH2)6NH2 n

Polyamide (nylon 6.6.)

SC CO2 P,T
Et H O O H H H H O C C S H H O N N N Et

O H HOOC(CH2)4 C N (CH2)6

N C (CH2)4 C N (CH2)6N n

no hydrolyzed by-products
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Sulfonyl-azo-dyes
Reactive Dye

Et Et

O S CH CH2 O
343.44

C18H21N Dye Non-Reactive 3O2S

Et Et N N O N S CH2 CH3 O C H NOS
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Dyeing Procedure
Add fiber and dye to vessel
Pressurize system (with CO2) up to 800 psi and stir at approximately 850 rpm

Heat to required temperature (100 -180 C)

Pressurize to 3500 psi; hold for 2 hours

Release pressure, remove fabric

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Testing Dye-Fiber Reaction

Measure color strength (K/S) of each dyed fiber Wash fiber with acetone (remove surface dye) Conduct soxhlet extraction using ethyl acetate (to remove unreacted dye) Compare effect of vinylsulfone reactive group on dye fixation

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Results
22 20 18 16
K/S value

Vinylsulfonyl-Dye Color Strength

Original VS-dyed wool Extracted VS-dyed wool
9.4% 6.2%

5.9%

14 12 10 8 6 4 2 0

26% 31%

100C

120C

140C

160C

180C

Dyeing Temperature
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Results
14 12 10
K/S value

Ethylsulfonyl-Dye Color Strength

Original wool fibers Extracted wool fibers
72.9% 77.9% 91% 92% 100C 120C 140C
Dyeing Temperature
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58.6%

8 6 4 2 0

160C

180C

Comparison of Dyed Fabrics

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Initial Conclusions
Color depth improved with increasing temperature
Strong evidence for dye-fiber bond formation using vinylsulfone-based dye on nylon and wool
ES-dyeing on wool fibers showed extremely low color yields after extraction (no reaction) 94% fixation at 180 oC/ 3500 psi on wool

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Acknowledgements

This research was conducted with the support of the NSF Green Processing Undergraduate Research Program with a grant from the National Science Foundation, Award Number, EEC-9912339.

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