Chemistry &

dyeing mechanisms

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Reactive Dyes
F
CHROMO -NHNH- ALIPH. BRIDGE -SO2 - CH = CH2

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General structure of a reactive

dye

SMA
C

RG

WSA

= The Chromophore

SMA = Shade modifying auxochromes

WSA = Water solubilising auxochromes
B

= Bridging group

RG

= Reactive Group

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Reactive dyes

CHROMO -NHNH- ALIPH. BRIDGE -SO2 - CH = CH2

Characteristics necessary for

continuous dyeing
Powder and liquid dyes
Excellent solubility
Excellent bath stability
Good compatibility and levelling
properties
Low-to-medium substantivity
Similar reactivity and rapid fixation
Unaffected by fixation time
variations
High degree of fixation
Excellent washing-off properties
Good fastness level
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Reactivity of the different

reactive groups
Cold dyeing

Hot
dyeing

Procion MX
Basilen M

Dichlortriazine

Difluorchlorpyrimidine
Monofluortriazine
Dichlorquinoxaline
Monofluortriazine
Vinylsulphone

Vinylsulphone
Monochlortriazine
Vinylsulphone

Monochlortriazine
Trichlorpyrimidine

Cibacron F
Levafix E-N

Levafix E

Cibacron C

Remazol
Sumifix

Sumifix Supra

Cibacron E
Procion H-E

Cibacron T-E
Drimaren Z

Increasing reactivity

Relative reaction speed

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Levafix E-A
Drimaren R, K

Monofunctional dyes
One reactive group
Monochlorotriazine

Chr

Cibacron E & P, Procion HE & P

Basilen E & P, Drimaren P

R
N

Cl

Monofluorotriazine

Chr

Cibacron F, Levafix E-N

R
N

Chr

Vinylsulphone
Remazol, Sumifix

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SO2-CH2-CH2-O-SO3H

Monofunctional dyes
Two reactive groups *
Cl
Chr

Trichlorpyrimidine
Cibacron T-E, Drimaren Z

Cl
N

Cl

Cl

Difluorochloropyrimidine

Chr

Levafix E-A, Drimaren K, R

N
F

Chr

Cl

Dichloroquinoxaline
Levafix E

Chr

Dichlorotriazine
Procion MX, Basilen M

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Cl

Cl
N

Cl

Fixation / hydrolysis of
monofunctional reactive dyes
Substitution reaction
OH
N

F
N
NH

OH

N
N

NH

CellO

N
R

OCell
N
NH

N
N

Addition reaction
--- CH2 - CH2 - O - SO3 H

- H2 SO4

OH

--- CH = CH2

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OH

CellO

--- CH2 - CH2 - OH

_
--- CH2 - CH2 - O - Cell

C.I. Reactive Blue 19

NH2
SO3Na

Non-vinylated form

N
H

SO2CH2CH2OSO3Na

+ Alkali
O

NH2
SO3Na

Vinylated form

SO2CH = CH2

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Homobifunctional dyes
Monofluorotriazine / Monofluorotriazine
Cibacron C
F

F
N

N
Chr

R1

Vinylsulphone / Vinylsulphone
Remazol, Cibacron C

SO2-CH2-CH2-O-SO3H
2HC

Chr

= CH-2OS

Monochlorotriazine / Monochlorotriazine
Cibacron E, Procion CX
Cl
N

N
Chr

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Cl

N
R

R1

Heterobifunctional dyes
Monofluorotriazine / Vinylsulphone
Cibacron C
F
N

N
Chr

NH-Aliph.bridge

S02-CH=CH2

Monochlorotriazine / Vinylsulphone
Sumifix Supra, Basilen FM, Cibacron W
Cl
N

SO2-CH2-CH2-O-SO3H
Chr

R
N

Fluorchlorpyrimidine / Vinylsulphone
Levafix ( Navy EBNA )
N

SO2-CH2-CH2-O-SO3H
N

Chr
Cl

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Colors
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R1 DYE R2

via R2

via R1

R1 DYE

OCell

R1 DYE OH

R2

DYE R2

HO DYE

CellO

DYE

OCell

OCell

DYE

HO DYE

CellO

OCell

DYE OH

HO DYE OH

CellO

CellO

Fixation / hydrolysis of a bireactive dye

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faster fixing than MCT reactive group higher reactivity

faster rate of fixation needs a lower pH for fixation.
the higher pH necessary to fix the MCT group endangers the
VS-fibre bond which is highly sensitive to alkaline hydrolysis
Thus,

This is a cause of poor repeatability

By ensuring that the MCT part of an MCT/VS bireactive dye fixes at a

reasonable rate, you endanger the VS fibre bond already formed due to
excessive pH. This is an unstable situation
Fixation and hydrolysis (destruction) of the bond at the same time !!

VS

MCT slower fixing than VS reactive group lower reactivity

needs a higher pH to fix at a reasonable speed
MCT-fibre bond is stable to alkaline hydrolysis

in MCT/VS dyes

The monochlorotriazine / vinylsulphone paradox

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slightly faster fixing than VS group higher reactivity

needs a slightly lower pH for fixation
FT-fibre bond is stable to alkaline hydrolysis

Any pH which is good enough to fix the VS group at a reasonable speed

is also high enough to fix the FT group as well.
No unnecessary endangering of the [VS/fibre] bond by excess of pH !!
This contributes to better repeatability

VS slightly slower fixing than FT reactive group lower

reactivity
needs a slightly higher pH for fixation
The lowest pH which fixes the VS group will also fix the FT
group, therefore, the VS-fibre bond is almost unaffected by
alkaline hydrolysis
Thus,

FT

in FT/VS dyes

Fluorotriazine/vinysulphone (as Cibacron C)

is a more logical bireactive system

Types of Polyreactive Dyes

Bridge
CHROMOPHORE

R1

R2

R1

R2

CHROMOPHORE

Head / Head
CHROMOPHORE

Head / Tail
R1

CHROMOPHORE

R2

Head / Bridge / Tail

R1

CHROMOPHORE

R2

CHROMOPHORE

Head / Head / Tail

R1

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CHROMOPHORE

R2

R3

R3

Parameters effecting the substantivity

and diffusion of a reactive dye by padding

dye
concentration

type of
fibre

time

dye
affinity

substantivity
diffusion

liquor
ratio

temperature

electrolyte
concentration
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pH

Tailing / Reverse Tailing

A change of colour strength and/or
shade along the length of the batch
Common causes:
Type of fibre

Insufficient or heterogeneous preparation

Variation in fabric temperature
Variations in drying temperature
Insufficient or excessive amounts of alkali
in the pad trough
A change of wet bulb temperature in
the steamer
non-uniform emerising effect
Main cause:
Affinity and diffusion coefficient of the dye:Tailing:- High affinity and/or too rapid diffusion
Reverse tailing:- Poor affinity and/or too slow diffusion

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