Md Rahat Ullah Rashed
Head Of Technical Support
Taiwan Persotex Ltd &
Taiwan TRS Ltd
Theory Of Polyamide Dyeing
Basic Concepts :
1. Uptake of Acid and Metal Complex dyes by Polyamide is temperature
dependent. The fibre takes up the dye at temperatures above the glass transition point
because the segments ( monomer ) in the polymer chains become more mobile at
higher temperatures. The fibre thus open and allow the dye, which is attracted to the
positive charge on the highly polar amino end groups ( NH2 ) in the fibre, to penetrate
the polyamide. It is then bonded to the fibre through intermolecular forces. Glass
Transition Temperature of Nylon 6 is 47 C and Nylon 6,6 is 70 C. Saturation ( Dye
Uptake ) of Polyamide Fibre may be 88% - 95%.
3. Polyamide Fibre is Cationic at Acetic Medium ( because -NH- is here ) but non
ionic at neutral or weakly alkali media and Anionic at over pH : 11.5. Acid Dyes are
Anionic. As a result Ionic Bond creates between fibre and dyes at acetic media.
4. Dyeing pH is low, exhaustion is quick, migration is low.
5. Dyeing pH is correct, colour yield is reached, migration is good, levelness is
good.
6. Dyeing pH is high, colour yield is lost, migration is good.
7. Dyeing final pH should be 5.0 - 5.5
8. Starting pH should be 7.5 - 8.0
9. These dyes combine with the fibre by hydrogen bonds, Van Der Walls Force or
through ionic linkages.
H-Bond ( between OH of Dyes and O of CONH from fibre )
Secondary Attractive Force
Protonation and Bonds
1. Nitrogen is less electronegative than Oxygen. So amide bonds in Nylon aren’t as polar as
hydroxides in Cotton. As a consequence Nylon is not as hydrophilic as Cotton but it is hydrophilic
enough to wick away sweat. The N-H groups are polar and make Nylon water loving.
2. Generally Nitrogen is more easily protonated than Oxygen because Nitrogen has one
loan pair electrons. The presence of more loan pairs in Oxygen makes it less available to
accept a proton compared to Nitrogen. Oxygen has two loan pairs of electrons which occupy
a larger region of space around the Oxygen Nucleus. This makes it more difficult for a proton
to approach and interact with the Oxygen atom. In contrast, Nitrogen has only one loan pair
of electrons which occupies a smaller region of space, leading to an easier interaction
between Nitrogen and the Proton.
3. Here 3 types of Bonds creates. These are Ionic Bond ( SO2 of Dyes and NH of fibre ),
H-Bond ( between OH of Dyes and O of CONH ( Amide Group ) or CO of Nylon 6 from fibre )
and Van Der Walls Force. Fastness mostly becomes poor due to H Bond and Van Der Walls
Force.
NOTE :
Amino Group : NH2
Amide Group : R-CO-NH2
Amine Group : R-NH2
Nylon 6 or Nylon 6,6 :
Nylon 6 is made of one monomer and
Nylon 6,6 is made of two monomers
each containing 6 carbon atoms of
Hexa methylene diamine and Adipic
Acid.
Above picture is Caprolactam. Caprolactam is the molecule
used to synthesis Nylon 6 by ring opening polymerisation.
Nylon 6 don’t has only one -CONH group ( Amide
Group ). So less H-Bond is formed in between
Dyes and -CONH of Nylon 6 which is seen more
in case of Nylon 6,6. As a result Wet Fastness of
Nylon 6 will be better than Nylon 6,6.
Fig : Acid Dye
Levelling Agent
In this monomer -O- is attached with another Carbon.
So structure is C-O-C. This is why it is Ether. Again R is
attached with Nitrogen. This is why it is Alkyl Amine.
This Polyoxyethylene Alkyl Amine is Non Ionic/Anionic
because at -OH oxygen atom will be negative end and
H atom will be positive end. As a result -OH will donate
proton and will be Anionic. At acidic condition Nitrogen
Atom receives Proton ( H+ ) because Nitrogen Atom has
Loan Pair Electron. Then it becomes Cationic. So a
affinity creates between Anionic Dyes and Cationic
Levelling Agent. At the same time Nylon Fibre becomes
Cationic at acetic medium. Between the Nitrogen atoms
( both Nylon and Levelling Agent ), Nylon will be
protonated easily compare to Levelling Agent. So dyes
will be attracted by fibre. At the same time dyes will also
be attracted by levelling agent but affinity between dyes
and fibre will be more. So dyes will move towards fibre
slowly because levelling agent will also attract dyes.
That means levelling agent retards dyes to be forwarded
towards fibre. So result is Level Dyeing. The bond
strength / affinity between Fibre - Dyes is more than the
bond strength / affinity between Dyes - Levelling Agent.
As a result Dyes will slowly move towards Fibre. To
make the affinity between Dyes - Levelling Agent less
than Dyes - Fibre, molecular weight of levelling agent
should be less than the molecular weight of fibre.
Why Polyamide can not
be dyed by Reactive
Dyes ?
Generally Polyamide is not dyed by Reactive Dyes. Reactive Dyes is not
sufficient substantive towards Polyamide Fibres because Polyamide fibre
don’t have Hydroxyl Group ( -OH ) like cellulose. Hydroxyl Group ( For having
it’s polarity ) of Cellulose makes the Reactive Dyes substantive towards
Cellulose. Due to polarity of Cellulose, cellulose makes the Reactive Dyes
Substantive towards itself where as Polyamide Fibre is not able to do it.
Moreover Reactive Dyes generally have a larger molecular size ( 400 - 1000
gm/mol ) than Acid Dyes ( 300- 500 gm/mol ). Nylon fibre structure is compact
and have no -OH group. So Reactive dyes can not penetrate into it easily.
Solubility Of Acid Dyes
It depends on below factors :
1. Lower molecular weight and more sulphonic acid groups ( Sulphonic acid group
makes the polar by making H-Bond with water i.e. soluble ), the higher solubility.
2. The easier the dye to Ionise, the higher it’s solubility.
3. The higher amount of electrolyte, reduce the solubility.
4. The higher temperature, higher solubility. Higher temperature increase the Kinetic
energy of Dyes.
5. The more OH, SO3H, NH2, NR2, NO2 etc Auxochrome makes the dye more
soluble.
6. In 1:1 metal complex Acid Dye, 3 coordination sites are occupied by metal,
whereas the remaining 3 coordination sites are occupied by Solvents like Water and
form H-Bond. That’s why 1:1 metal complex acid dyes are more soluble than 1: 2 metal
complex Acid Dyes.
It’s better migrate at 95 C
maintaining pH 7.5 - 8.0 and
run for 20 minutes ( Here
migration will happen and
undissolved Dyes will be
dissolved also ) then cool it to
50 C and dose the acid to
maintain proper pH. After this
run at 98 C for fixation. In this
way better levelness will be
found.
Polyamide Fixing
In 1:1 metal complex Acid Dye, 3 coordination sites of
metal are occupied by Dye whereas the remaining 3
coordination sites are occupied by Solvents like Water and
form H-Bond. That’s why 1:1 metal complex acid dyes are
more soluble than 1: 2 metal complex Acid Dyes.
Thank You
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