Colo 5020 Physical Chemistry of Coloration Wool

Further reading
Wool Dyeing, Ed. David M Lewis. Society of Dyers & Colourists, Bradford, 1992 Contents Chapter 1 The structure of wool, Chapter 2 The theoretical basis for wool dyeing, Chapter 3 The role of auxiliaries in wool dyeing, Chapter 4 Ancillary processes in wool dyeing, Chapter 5 Wool-dyeing machinery, Chapter 6 Dyeing wool with acid and chrome dyes, Chapter 7 Dyeing wool with metal-complex dyes, Chapter 8 Dyeing wool with reactive dyes, Chapter 9 Dyeing wool blends, Chapter 10 Wool printing, 384 pages, ISBN 0 901956 53 8

Production process

Loose Stock

Yarn

Piece

Garment

Methods of colouring wool

Wool Fibre

Tip

Root

Morphology of Wool Fibre

Morphology of Wool Fibre

Simple schematic of wool fibre

Chemistry of Wool Fibre

The basic amino acid residues in wool are arginine, lysine and histidine, which total about 900mol g-1. These are predominant dye sites for the attraction of acid dyes to wool

18 L-alpha-amino acids L-alpha1 imino acid (proline) peptide bonds

NH NH 2 R COOH + NH 2 R
1

R CO peptide link NH R1 CO

COOH

Polymer of approx. 600 amino acids; Keratin

The chemistry of wool

Hydroxyl (serine)
NH 2 HO-CH 2-CH COOH

hydrocarbon (glycine)
NH 2 H-CH

phenolic (tyrosine)
NH 2 HO CH 2-CH COOH

COOH

Basic (lysine)
NH 2 H 2N-(CH 2)4-CH COOH

Acidic (aspartic acid)

NH 2 HOOC-CH 2-CH COOH

amino acids

Chemistry of Wool Fibre

Chemical groups found in the fibre and bonds ie disulphide etc How wool is damaged, alkalinity and how this affects the chemical bonds Within the fibre

Wool Fibre : Scouring

Why? remove Impurities on surface: grease, dirt etc Prepare for further processes e.g shrink resist/dyeing Method of scouring: chemicals time and temp, pH

Wool Fibre : Shrink resist processes

Why shrink resist is necessary: stabilise fibre to mechanical action during dyeing and post processes Explaination of how wool shrinks: relaxation shrinkage & felting shrinkage Bring in: Chlorination and development of this process Chlorination plus polymer treatments: Early GRB type processes Problems with polymer processes on colouration ie levelness problems, reduced fastness propoerties

NH H 3N + -(CH 2)4-CH CO lysi e resi ue

Ionic

CH-CH 2-COO CO as artic aci resi ue

NH

H O

NH HO-CH 2-CH CO Seri e resi ue

H bonding

HC-H 2C CO yr si e resi ue
NH 2

NH 2

NH

NH

Disulphide

CH-CH 2-S-S-CH 2-CH COOH Cysti e COOH

CH-CH 2-S-S-CH 2-CH CO CO

Inter-molecular interactions

Water absorption of wool

F ib re c o tto v is c o s e ra y o w ool s il c e llu lo s e ia c e ta te n y lo n 6 .6 a c ry lic c e llu lo s e tria c e ta te o ly e s te r % H 2O re g a i 2 1 oC ; 6 5 % H 8 .5 1 1 .5 - 1 6 .6 17 11 6 .4 4 - 4 .5 1 -2 4 0 .4 % H 2O s e lli g 4 4 -4 9 4 5 -8 2 3 2 -3 8 3 0 -4 1 6 -3 0 2 s lig h t v e ry s lig h t n il

Dyes for Wool

Acid dyes PrePre-metallised acid dyes Mordant (chrome) dyes Reactive dyes

Dyes used

Acid dyes

O N N O -S O O OH N CH3 O S O O

Acid dyes contain water solubilising sulphonate groups (anionic groups)

Dye - fibre interactions

Consider the chemistry of wool...

Wool contains amino groups and carboxylic acid groups

H 2N
At pH 7 (neutral) the wool exists as a zwitterion

CO2H

+H3N

CO
2

In acidic pH conditions....

the carboxylic acid is protonated

+H3N

CO2H

the amine is protonated

In alkaline pH conditions

the carboxylic acid is deprotonated

H 2N

CO2-

the amino group is deprotonated

Thus, at pH 7 (neutral) the wool can interact with an anionic acid dye by ion-ion intermolecular interaction between the anionic sulphonate group of the dye and the cationic protonated amino group.

SO3

Electrostatic interaction

+H

3N

Similarly, in acidic pH conditions the protein can interact in the same way.

SO3

Electrostatic interaction

+H

3N

Effect of pH on the dissociation of Glycine in aqueous solution

H+

H NH
+

H NH2

NH

OH-

NH2

100

COOH COO-

NH3+ NH2

50 pH 0 2.35 = pK (COOH) 9.78 = pK(NH2) 12

Effect of pH on the issociation of Glycine in aqueous solution

PH 0.35 1.35 2.35 3.35 4.35 7.78 8.78 9.78 10.78 11.78

COOH 99.01 90.91 50 9.09 0.99 0 0 0 0 0

COO0.99 9.09 50 90.91 99.01 100 100 100 100 100

NH3 100 100 100 100 100 99.01 90.91 50 9.09 0.99

NH2 0 0 0 0 0 0.99 9.09 50 90.91 99.01

pK(NH2) = 9.78

pK (COOH) = 2.35

(non(non-metallised) acid dyes prepre-metallised acid dyes mordant dyes reactive dyes

Dyes used

acid levelling

intermediate

acid milling

molecular size increases fastness to aqueous agencies increases application pH increases affinity increases

3 types of non-metallised acid dyes non-

acid dyes: wash fastness properties

acid levelling intermediate acid milling

molecular size increases fastness to aqueous agencies increases

ISO CO3 (wash fastness test) acid levelling intermediate acid milling 1 3 5

9
Worsening wash fastness

Grey scale rating

5
acid milling

3
intermediate acid levelling

RELEVANCE OF HYDROPHOBIC INTERACTIONS TO WOOL DYEING

Consider two acid dyes with different hydrophobicity..

O N N O -S O O OH H CH O S O O O CH HN HO N N O S - O O O S O O

Lissamine Red 2G acid levelling

Carbolan Red B acid milling

H C

ISO CO3 (wash fastness test) acid levelling intermediate acid milling 1 3 5

9Red 2G Lissamine 9Red B Carbolan

Only ifference is the hy rophobic chain !

prepre-metallised acid dyes

METAL

HH

CH3

1:1 complex

HO

O S O N N OH HN

O OH S O CH3 O

METAL
O N N O S HO O OH HN CH3 O S OH O

2:1 complex

prepre-metallised acid dyes dyeing mechanism

O N N O -S O O OH HN CH3 O S O O H +H N H H +H N H

H O

Electrostatic.same as non-metallised acid dyes!

O OH

Mordant dyes
Conventional acid dyes BUT mordant (metal) added after dyeing with conventional acid dye

WOOL
O OH H O S OH O O S OH O

O H

WOOL coloure with aci ye

METAL mor ant added

O OH H O S O OH O S O OH

O H

aggregation

Chrome dyeing is an example of mordant dyeing...

Na2Cr2O7 (anionic, therefore rapidly absorbed)

Reduction of CrVI to Cr III by cystine in the fibre, which is oxidised). The Cr III complexes with the dye

Reactive dyes
Reactive group
2 2

S
2

Reactive dyes

Wool contains amino groups and carboxylic acid groups

H 2N

CO2H

Dyeing mechanism

In alkaline pH conditions

the carboxylic acid is deprotonated

H 2N

CO2-

the amino group is deprotonated

O S O N OH NH2 N N N O O S S HO O O OH

H2

Nucleophilic addition

H 2N

Michael reaction

WOOL-NH-CH2CH2SO2-DYE

CH2 O S O N OH NH2 N N N O O S S HO O O OH

O S O

CH2

Nucleophilic addition

HS

WOOL-S-CH2CH2SO2-DYE

Types of reactive dyes Sulphatoethyl sulphone (Vinyl sulphone) Triazine based (Monochloro triazine) Acrylamido based (E bromo acrylimido) (E

vinyl sulphone reactive dyes

CH O S O OH O S HO O H O S O OH O S O CH

Vinyl group (CH2=CH)

sulphone group (SO2)

vinyl sulphone reactive dyes

CH O S O OH O S HO O H O S O OH O S O CH

Nucleophilic addition

H 2N

Michael reaction

WOOL-NH-CH2CH2SO2-DYE

Triazine reactive dyes

Cl N Dye N N Cl
3 nitrogens : latin for nitrogen is aza i.e. triazine

Triazine reactive dyes

Cl N Dye N N Cl
H 2N Nucleophilic substitution

Cl N Dye N N
HN

acrylamido reactive dyes

Dy

NH O CH2
Amide group (NHCO)

Acryl group (CH2=CHCO)

acrylamido reactive dyes

Dy NH O CH2
H 2N Nucleophilic addition

Michael reaction

Dye NH O H2
HN

Summary of dyes used on wool

Dye type

Shades available

Wash fastness

Light fastness

non-metallised acid bright, wide gamut 1:1 pre-metallised acid 2:1 pre-metallised acid mordant reactive dull, widish gamut dull, widish gamut dull, widish gamut

low-very good poor

low-good moderate-good moderate-good very good/excellent

good-very good excellent

bright, widish gamutvery good good/very good