doi: 10.1111/cote.

12391

Effects of the side chain density of

polycarboxylate dispersants on dye Coloration
dispersion properties Technology
Hamid Gharanjig,a,b Kamaladin Gharanjig b,c
* and
Alireza Khosravia
a
Department of Polymer Engineering and Color Technology, Amirkabir University of
Technology, No.424, Hafez Ave., Tehran, Iran, 15875-4413
Email: gharanjig@icrc.ac.ir
Society of Dyers and Colourists
2
Department of Organic Colourants, Institute for Color Science and Technology, No.55,
Vafamanesh St., Tehran, Iran, 16765-654
3
Center of Excellence for Color Science and Technology, No.55, Vafamanesh St., Tehran, Iran,
16765-654.
Received: 10 April 2018; Accepted: 15 January 2019

Comb-like polycarboxylates were synthesised by copolymerisation of methacrylic acid and nonylphenol

polyethylene glycol methacrylate ester, and can be used as dye dispersants. In order to achieve good
dispersive ability, three polycarboxylates were synthesised, each having a different side chain density. The side
chain density of polymers was controlled by different ratios of monomers in the copolymerisation process.
Acidic polymers were neutralised using sodium hydroxide. These polymers exhibit good dispersing
performance, such that carboxylate groups are adsorbed onto the dye particle surface and the side chains
enable the formation of a thick layer, thus providing the steric hindrance effect. Improvement of dye dissolution
in the presence of polycarboxylates was studied. Polymers with a lower side chain density demonstrated a
higher dye dissolution in water, which could be as a result of more effective adsorption of dispersant on the dye
surface (CI Disperse Blue 79). The dyeing performance of the prepared dye dispersions on polyester was
investigated. Spectrophotometric analysis of dyed fabrics using synthesised polycarboxylates demonstrates
that there should be an optimum side chain density of polymer in order to control both dye solubility and
dispersive ability. The result of turbidimetry and particle size analysis have proven this phenomenon. A comb-
like polycarboxylate with optimum side chain density was a better dye dispersant compared with a commercial
sodium naphthalene sulphonate compound, as a result of its better heat stability.

studies regarding using polycarboxylates to disperse kaolin

Introduction
Dispersants are chemicals which migrate to solid–liquid
interfaces and cause stability among solid particles in liquid
media [1]. Change in the surface free energy of solid particles
is the main mechanism of dispersion for dispersants of low
molecular weight [2]. Dispersants of high molecular weight
have anchor groups which afford strong adsorption of the
polymer onto the particle [3]. Their long molecular chains
can create the steric hindrance effect. This is because of loops
or tails which arise when the polymer is adsorbed onto the
particle surface [3,4]. Average molecular weight, molecular
weight distribution, solubility, anchor groups, and the
configuration of polymers are key factors for polymeric
dispersants to disperse particles [5–8].
There is a strong tendency to use polycarboxylates in
concrete, ceramics and paints as polymeric dispersants
[9–11]. Polycarboxylates are homopolymers or copolymers
of monomers containing carboxylic acid groups, for example,
(meth)acrylic acid, maleic anhydride and itaconic acid
[12,13]. Water-soluble comb-like polycarboxylates contain
polyethylene or polypropylene oxide side chains which are
attached to the backbone [14]. They can adsorb onto solid
particles by electrostatic attraction, hydrogen bonding or van
der Waals interactions [15,16]. Side chains are responsible
for the steric hindrance effect [17,18]. Chemical moiety and
the length of side chains, side chain density and the
molecular weight of the dispersant are important variables
in the design of polycarboxylate dispersants [18–21].
The application of polycarboxylates as cement super-
plasticisers has been studied [17–21]. There have also been
particles in ceramics [10,22,23].
The use of dispersants is essential in the dyeing of
synthetic fibres with disperse dyes [24,25]. Polymeric
dispersants have recently been applied in dyeing to improve
dyeing properties [26–29]. Sodium polynaphthalene sul-
phonic formaldehyde (PNS) and polyoxyethylene sorbitan
ester-based dispersants were used to disperse quinizarin.
Results of turbidimetry and particle size analysis of dye
dispersions showed that both of these dispersants demon-
strated good dispersibility [28]. Hydroxypropyl sulphonated
lignin was used as a dye dispersant. The effect upon average
molecular weight was investigated, and it was shown that
hydroxypropyl sulphonated lignin has better dispersability
than sodium PNS, as a result of better heat resistance [29].
In this study, different dispersants based on polycar-
boxylate were synthesised. Dispersants have different side
chain densities. Dye suspensions were prepared under
different conditions using synthesised and commercial
dispersants. Turbidimetry and particle size of the dye
dispersions were tested. Also, the application of polycar-
boxylate as a dye dispersant is reported. The effect of the
side chain density of polycarboxylates for a previously
cementitious mixture is reported [17–20].
Experimental
Chemicals and apparatus
Methacrylic acid (MA) and nonylphenol polyethylene
glycol (NP-10, n = 10) of industrial grade were purchased
from Lucite International (UK) and Kimiagaran Emrooz

© 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9 1
Gharanjig et al. Polycarboxylate dispersing agents

Chemical Industries (Iran), respectively. Toluene-4-sulpho- Purification was confirmed using TLC and differential
nic acid sodium salt, phenothiazine and 3-Mercapto propi- scanning calorimetry (DSC). TLC was performed on silica
onic acid were purchased from Merck (USA). Cyclohexane gel eluded with a mixture of 2:1 ethyl acetate:n-hexane. The
and ammonium persulphate were provided by Petrochem purified dye gave a single spot such that the retention factor
(UAE) and BASF (Germany), respectively. CI Disperse Blue was Rf = 0.74. The DSC shows only one peak, which is
79 and sodium PNS were supplied by Enacol (Africa) and related to the dye mp at 146 °C. The DSC graph is shown in
DyStar (Singapore), respectively. Figure 2. Dye suspensions were prepared using different
Fourier Transform-infrared (FTIR) spectroscopy was concentrations of the dispersants used. They were stirred in
performed on a Perkin Elmer device. Gel permeation an Incubator shaker at 25, 45 and 65 °C. Sampling was
chromatography was performed on a Shimadzu LC appara- performed over time while the dye dispersions were being
tus equipped with RI detector and Waters ultrahydrogel shaken. Then they were filtered and dissolved in acetone for
linear columns with an operating range (polyethylene ultraviolet-visible (UV-Vis) spectroscopy. The measured
oxide) of Mw = 100–1 000 000 Da, according to ASTM wavelength of maximum absorbance and the molar extinc-
D5296; 0.1 M sodium nitrate at pH 12 was used as eluent. tion coefficient of the blue dye were 580 nm and
Absorption spectroscopy was performed on Cecil CE9200 46 400 dm3/mol/cm, respectively. The concentration of
(UK). Reflectance measurements were performed on dyed dissolved dye was calculated by Beer-Lambert law [30].
fabrics using a XRite SP64 spectrophotometer. Turbidime- Dye suspension values are listed in Table 3.
try and particle size analyses were performed by Hach
2100N and Malvern instruments, respectively. Dyeing of Optimisation of dispersant concentration
fabrics was carried out using a Rapid dyeing machine. Dye dispersions were prepared by the solution method
using different dispersant concentrations. A similar method
Synthesis of dispersants has been reported previously [28]. Dyeing of polyester
Nonylphenol polyethylene glycol monoacrylate ester was fabrics was carried out with the high temperature method.
synthesised by esterification of MA with 33 g NP-10. The For this purpose, the dyebath temperature was raised from
reaction proceeded with an equivalent molar ratio of 30 to 90 °C at 2 °C/min, followed by 90–130 °C at 1 °C/min,
reagents. Toluene-4-sulphonic acid sodium salt (0.5 g), maintained at 130 °C for 60 min, and then cooled to 70 °C
cyclohexane (5 g) and phenothiazine (0.01 g) were used as
the esterification catalyst, dehydrating agent and polymeri-
sation inhibitor. The reaction proceeded at 85 °C and the Table 2 Chemicals and their quantities for polycarboxylate
water formed was removed by Dean-Stark apparatus. At the synthesis
end of the reaction (confirmed by thin-layer chromatogra-
phy [TLC]), cyclohexane was removed from the macro- Content, g
monomer.
Next, the macromonomer was copolymerised with dif- Chemical PD1:2 PD1:3 PD1:4
ferent concentrations of MA. Macromonomer to MA ratios
are reported in Table 1. Copolymerisation was carried out Macromonomer 15.76 15.76 13
using ammonium persulphate in aqueous media at 80 °C; 3- Methacrylic acid 4 6 6.75
3-Mercapto propionic acid 0.30 0.30 0.30
Mercapto propionic acid was used as the chain transfer
Ammonium persulphate 0.22 0.22 0.22
agent. This resulted in different polycarboxylic acids with Water 23.10 23.10 23.60
different side chain densities. All of the chemicals and their Sodium hydroxide (50%) 3.70 5.85 9.40
quantities are listed in Table 2. The synthesised polymers
were neutralised with aqueous sodium hydroxide. The
solid content of dispersants was fixed at 35%. The chemical
COOH CH3
structure of the synthesised polycarboxylates is shown in
Figure 1. * CH2 C CH2 C *
y
Solubility of CI Disperse Blue 79 CH3 x
O
CI Disperse Blue 79 was purified by Soxhlet extractor with O
acetone as the extraction solvent to remove the dispersing
agent and impurities from the dye. The resulting dye was x/y = 4 PD1:4
dried by rotary evaporation. Then it was recrystallised in
ethanol, filtered (Whatman grade 42 filter paper), and dried. x/y = 3 PD1:3
O
x/y = 2 PD1:2
Table 1 Specification of polycarboxylate dispersants n

n = 10
Polycarboxylate Macromonomer: Mw, Polydispersity
dispersant MA ratio g/mol Index

PD1:2 1:2 10 000 1.21

PD1:3 1:3 15 000 1.27 C9H19
PD1:4 1:4 17 000 1.33
Figure 1 Chemical structure of synthesised polycarboxylates

2 © 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9
 Gharanjig et al. Polycarboxylate dispersing agents

at 3 °C/min. Dyebath ingredients are given in Table 4. After
dyeing, reduction clearing was performed using 3 g/l
sodium hydrosulphite, 2 g/l sodium hydroxide and Liquor
ratio (L:R=50:1) for 20 min at 70 °C.
Dye dispersion stability
Dye dispersions were prepared by milling the used disperse
dye in the presence of the optimum concentration of
dispersants. According to results, the optimum concentra-
tion of polycarboxylates is 2.5% omf, while for PNS it is
0.5% omf. Milling was performed for 20 h in a ballmill. Dye
dispersions were then diluted for further analysis.
Measurement of build-up
Dyeing was conducted using optimum concentrations of
dispersants and various dye concentrations, which were
0.5%, 0.8%, 1.2%, 2% and 4% omf. Reduction clearing was
carried out after dyeing. Reflectance spectrophotometry was
then performed on dyed fabrics. The K/S of the dyed fabrics
was estimated using the Kubelka–Munk equation.
Investigation of the heat stability of dye dispersions
In order to investigate the heat stability of dye dispersions,
dyeing was carried out, except that the polyester fabrics
were not added to the dyebath. Dye dispersions with the
optimum concentration of dispersant were prepared using
the milling method. Then the dye dispersions were heated
to 130 °C in a dyeing machine. Finally, sampling was
carried out for turbidimetry, particle size analysis and dye
solubility measurements.
Results and Discussion
Characterisation
FTIR was performed on the macromonomer, MA and NP-10
(Figure 3). The macromonomer was synthesised by esteri-
fication of the carboxylic acid group of MA and the
hydroxyl group of NP-10, which resulted in an ester group.
The peaks for ester groups are at ca. 1740 cm
1 for (C=O)
and between 1100–1300 cm
1 for (C–O). The (C=O) of
carboxylic acid has peaks in similar regions. Therefore, it is
not possible to confirm that an ester has been fully formed.
The broad peak at ca. 3500–2800 cm
1 disappeared in the
macromonomer spectrum, which is related to the hydroxyl
of carboxylic acid. This indicates that there is no carboxylic
acid in the product residue. However, there is no specific
peak which shows MA polymerisation or other possible
side reactions. Gel permeation chromatography (GPC) was
performed on synthesised polymers to characterise their
molecular weight and molecular weight distribution
(Table 1).

DSC, µV/mg Dye solubility

↑ exo
[1] CI Disperse Blue 79 has very low solubility in water.
0
Samples were prepared by adding the purified dye powder
to water in the absence of dispersants. They were stirred
–2
and heated using shaker and incubator. The concentration
of dissolved dye in water was measured over time. Results
–4 revealed that there was almost no solubility of dye at 25 °C
over time. The solubility of dye at 45 and 65 °C is shown in
–6 Figure 4. The solubility of dye increased with increasing
temperature. This phenomenon could be ascribed to acti-
–8 vation energy, according to the Arrhenius equation. Similar
Peak: 146.0°C findings have previously been reported [31–33]. Dye disso-
–10 lution increased by increasing time and temperature.
100 120 140 160 180 200 220 240 Dye dissolution also increased through the addition of
Temperature, °C dispersant. The enhancement of dissolution was negligible at
25 and 45 °C. Dye dissolution in the presence of polycar-
Figure 2 DSC thermogram of purified CI Disperse Blue 79 boxylate dispersant (PD)1:4 at 65 °C is shown in Figure 5.
Solubility results show that dispersant concentration has a
significant effect on dye dissolution. The maximum dissolu-
Table 3 Values for dye suspension preparation tion of disperse dye was <0.9 mg/l without dispersant, while
in the presence of PD1:4 the dissolution increased to ca.
Sample 1 2 3 4 5 2 mg/l. By increasing dispersant concentration, the solubility
of dye was increased to ca. 6 mg/l. An appropriate polymeric
Dispersant, g/l 0 0.5 1 2 4 dispersant concentration is needed to cover the particle
Dye, g/l 1 surface in order to avoid particle agglomeration. This results
in the production of particles with a lower size. According to
the Ostwald relationship, the lower the particle size, the
greater the solubility [34]. The effect of dispersants on
Table 4 Dyebath ingredients improving the solubility of disperse dyes has been reported
elsewhere [35–37].
Sample 1 2 3 4 5 6 The impact of dye dissolution in the presence of different
dispersants at a concentration of 4 g/l was investigated
Dye:dispersant ratio 2:1 1:1 1:2 1:3 1:4 1:5 (Figure 6). Among dispersants, PD1:4 performed best at
L:R = 50:1 Dye = 0.5% omf Polyester = 1 g increasing dye solubility. This could be because of effective
adsorption of PD1:4 onto dye particles. Higher side chain

© 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9 3
Gharanjig et al. Polycarboxylate dispersing agents

100.0

98

96

94

92

90

88
Transmittance

c
86

84

82

80

78

76

74 a b

72

69.3
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
Wave number, cm–1

Figure 3 FTIR spectra of (a) macromonomer, (b) MA and (c) NP-10

45 65 Linear (45) Linear (65)

0.9

0.8

0.7

0.6
C, mg/l

0.5

0.4

0.3

0.2

0.1
4.5 5 5.5 6 6.5 7 7.5 8
ln, t

Figure 4 Dissolution of disperse dye in water over time (min) without dispersants at 45 and 65 °C

density makes the dispersant more hydrophilic. On the are reported in Table 5. The calculations were performed
other hand, dispersants with a higher side chain density using Eqns 2 and 3 [38]. j and j0 are proportional to dye
have fewer carboxylate groups on the polymer backbone. solubility and the rate constant of the process; ln (j0 /j) is a
Because the carboxylate group may interact with dye constant value.
 0
molecules, reducing the number of carboxylates results in j
C ¼ ln þ j lnðtÞ ð1Þ
lower adsorption. Carboxylate groups play an important j
role in interacting with functional groups of dye molecules
through hydrogen bonding. Similarly, less adsorption of j
r¼ ð2Þ
polycarboxylates with higher side chain densities has been t
reported for cement particles [17,20].
Cs
As can be seen from Figures 3–5, the concentration of j¼ ð3Þ
lnðS0 =Ss Þ
dye was depicted vs logarithm of time according to Eqn 1.
The linear plot of the dye concentrations validates the where t and Cs are time and saturation concentration,
exponential equation. Kinetic parameters for dye solubility respectively, S0 and Ss are the initial surface area of the

4 © 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9
 Gharanjig et al. Polycarboxylate dispersing agents

7
0.5 g/l 1 g/l 2 g/l 4 g/l

C, mg/l
3

0
3 4 5 6 7 8
ln, t

Figure 5 Effect of concentration of PD1:4 on dye dissolution over time (min) at 65 °C

PD1:2 PD1:3 PNS PD1:4

7

4
C, mg/l

0
3 4 5 6 7 8
ln, t

Figure 6 Effect of different dispersants on dye dissolution over time (min) at 65 °C

Table 5 Kinetic parameters for dye dissolution at 65 °C in the

presence of 4 g/l dispersant Effect of dispersant concentration on dyeing
Polyester fabrics were dyed using different concentrations
r. 103 of dispersants. The results of reflectance spectrophotometry
3 3
r. 10 r. 10 (mg/h) for dyed fabrics are reported in Figure 7. In all samples, the
j, (mg/h) (mg/h) at t = greater the polycarboxylate concentration, the higher the K/S
Dispersant mg/l r2
Cfinal at t = 2 h at t = 8 h 30 h
value that is obtained. As was reported in the previous
section, increasing PD causes an increase in dye solubility.
PD1:4 1.291 0.98 6.06 64.565 16.141 4.304
Because dye transfer to polyester takes place in a monomolec-
PD1:3 0.340 0.99 2.05 17.015 4.254 1.134
PD1:2 0.252 0.96 1.89 12.600 3.150 0.840 ular aqueous solution [39], the dye concentration in fibre
PNS 0.753 0.94 4.69 37.655 9.414 2.510 therefore increases. However, there is an optimum concen-
tration for PNS, which causes a limitation in achieving higher
values of K/S.
To provide a better comparison among dispersants,
solute and the surface area of the solute at the saturation spectrophotometry of dyed fabrics with the optimum
concentration, respectively, S0/Ss shows the reduction of concentration of dispersants was performed (Figure 8). As
accessible dye surface during dissolution [38], and Cfinal is can be seen, the highest K/S value was achieved by PD1:3.
the maximum measured concentration of dye at the This shows that there is an optimum side chain density for
finishing point . polycarboxylates as a dyeing auxiliary. The mechanism of
The solution containing PD1:4 had the highest j value, dispersion for PD is electro-steric. Side chains have the
which shows that this dispersant had the greatest main role in providing steric hindrance. Nevertheless,
impact upon dye dissolution. According to Table 5, the higher side chain density leads to greater steric hindrance
rate of dye dissolution is significant initially but decreases effect [14,20]. However, higher side chain density causes
over time. less effective adsorption of PD [17,20]. Unlike the dye

© 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9 5
Gharanjig et al. Polycarboxylate dispersing agents

dissolution results, PD1:4 was not the best dispersant for
dyeing polyester. According to the comparison of Cfinal
values in Table 5, the solubility effect of PD1:4 for CI
Disperse Blue 79 is three times stronger than that of PD1:3.
This may influence the hydrophilicity of dyes. As polyester
fibres have a hydrophobic nature, high solubility of dyes
would have a negative effect upon dye transfer to polyester.
Considering the solubility results, all PDs demonstrated
better dispersing ability than PNS, which could be because
of their better performance at high temperatures.
Dye dispersion stability
Dispersants with good dispersive ability prevent dye
agglomeration and lead to the production of dispersions
with small particle sizes. Particle size analysis of dye
dispersions was performed (Figure 9). Average particle
sizes (d(0.5)) for PNS, PD1:2, PD1:3 and PD1:4 are 3.6, 2.9,
3.3 and 3.1 lm, respectively. According to the results, all of
the dispersants have the ability to prevent dye agglomera-
tion, but not all of the dispersants demonstrate a similar
efficiency in reducing particle size. However, it is not
possible to compare all of the dispersants simultaneously. A
suitable dispersant may stabilise particles for a longer time.
This could be measured using turbidimetry. The higher the
turbidity value, the smaller the size of the particles [40,41].
The results of dye dispersions are shown in Figure 10.
PD1:3 has a higher initial and final turbidity. This means
that PD1:3 has the ability to disperse dye particles and
stabilise them over time. Unlike the dyeing results, PNS had
a better dispersion stability than PD1:2 and PD1:4. A

C1 21 C1
18 (a) C2 (b) C2
C3 18 C3
15 C4 C4
C5 15 C5
12 C6 C6
12
K/S
K/S

9
9
6 6
3 3
0 0
400 500 600 700 400 500 600 700
Wavelength, nm Wavelength, nm

12 C1 10 C1
(c) C2 (d) C2
C3 C3
10 C4
C5 8 C4
8 C6 C5
6 C6
K/S

K/S

6
4
4

2 2

0 0
400 500 600 700 400 500 600 700
Wavelength, nm Wavelength, nm

Figure 7 Effect of dispersant concentration on K/S; (a) PD1:4, (b) PD1:3, (c) PD1:2 and (d) PNS; C1–C6 are 0.25%, 0.5%, 1%, 1.5%, 2% and
2.5% omf, respectively, and the dye concentration is 0.5% omf

20 PNS
18 PD1:4
PD1:2
16
PD1:3
14
12
K/S

10
8
6
4
2
0
400 450 500 550 600 650 700
Wavelength, nm

Figure 8 Effect of dispersant nature on K/S

6 © 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9

negative effect of heat on PNS is possible. Low heat
resistance of PNS has been demonstrated [29].
Effect of polycarboxylates on build-up
In order to gain good dye uptake and dyeing properties, a
dyebath with good colloidal stability and high temperature
stability is needed during the dyeing process [28,42].
Dyeing was completed on polyester fabrics using different
concentrations of dye. The dispersant dose was optimal.
The results of reflectance spectrophotometry are shown in
Figure 11. As can be seen, PD1:3 has the best build-up
effect. It produced greater K/S at different dye concentra-
tions and achieved dye saturation on fabric at lower dye
concentrations in a dyebath. As K/S is equal to the dye
concentration on fabric, PDs therefore performed better at
transferring dye onto the fibres. All of the results, including
investigation of the effect of dispersants’ concentration
upon K/S and build-up, are of the same order. PD1:3 is the
best dispersant and displays significant differences to the
other dispersants. Because visual evidence is a key factor
for dye dispersants, photographs of the dyed samples are
shown in Table 6.
4
Volume, %
0
0.1 1 10
PNS
Figure 9 Particle size distribution of dye dispersions prepared by different dispersants
1300
PNS
1200
1100
Turbidity, NTU
1000
900
800
700
600
0 50
Figure 10 Turbidity values for dye dispersions prepared by different dispersants
© 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9
Gharanjig et al. Polycarboxylate dispersing agents
Effect of polycarboxylates on the heat stability of dye
dispersions
In order to discover the advantages of PDs over commercial
PNS, prepared dye dispersions with different dispersants
were heated to 130 °C in a dyeing machine. Then tur-
bidimetry, particle size analysis and dye solubility mea-
surements were performed on cooled dispersions (Table 7).
This shows that average particle size increased for PNS and
that there was also a reduction in turbidity values for PNS,
whereas dispersions prepared with PDs have higher tur-
bidity values and a lower particle size. Therefore, the
performance of PNS decreases at high temperatures. The
poor heat stability of PNS at 130 °C was reported by
investigating the sediment thickness of dyebaths [29]. Poor
heat stability of dispersants causes agglomeration of dyes,
which prevents them from penetrating into fibres. In
practice, the wastewater of all dyeing samples is colourless,
which at first shows dye transfer to the fibres. But deposits
of agglomerates on fabrics or dyeing machines can be seen
during the reduction clearing process or when washing the
dye machine. Nevertheless, the dispersant should have the
100 1000
Particle size, µm
PD1:2 PD1:3 PD1:4
PD1:3 PD1:2 PD1:4
100 150
Time, min
7
Gharanjig et al. Polycarboxylate dispersing agents

PNS PD1:2 PD1:3 PD1:4

30

25

20
K/S

15

10

0
0 1 2 3
Dye concentration, % omf

Figure 11 Effect of dispersant nature on K/S

Table 6 Effect of dispersant and dye concentration on K/S

Dye, % omf PD1:2 PD1:3 PD1:4 PNS

0.1

0.8

1.2

ability to prevent dye agglomeration, even at high temper- Table 7 Effect of dispersants on heat stability of dispersions
atures.
Average
Absorbance particle Turbidity Turbidity
Conclusion Dispersant at 580 nm size, lm (initial) (after 2 h)
Polycarboxylates were used as dye dispersants. Three PDs
were synthesised with different side chain densities. Two PD1:2 0.20 1.9 413 264
types of experiments were carried out on different disper- PD1:3 0.24 1.7 453 268
sants. One of the experiments occurred on dye suspensions PD1:4 0.19 2.1 432 224
PNS 0.16 5.3 220 122
and the other experiment was performed on dyed fibres

8 © 2019 The Authors. Coloration Technology © 2019 Society of Dyers and Colourists, Color. Technol., 0, 1–9

using different dispersants. Dye dispersions were prepared
using polycarboxylates and a commercial dispersant. Tur-
bidimetry and particle size analysis results showed that all
dispersants have the ability to prevent dye agglomeration.
Dye dissolution studies showed that PD1:4 gave the best
performance in terms of improving dye dissolution. This
could be because of more carboxylate groups on the
polymer backbone, which results in efficient adsorption
on the dye particle surface. Except for solubility, all of the
other experiments showed a better performance of PD1:3
compared with the other dispersants. Results of dyeing
indicated that PD1:3 is the best dye dispersant. This could
be because of an optimised molecular architecture of PD1:3.
It causes both good adsorption of dispersant on the dye
surface and an effective steric hindrance effect. PD1:4 was
not as efficient as PD1:3 in dyeing polyester because it
increased dye solubility in such a way that the affinity of
dye to polyester decreased. The optimum concentration for
PNS was 0.5% omf, whereas the value for polycarboxylates
was 2.5% omf. This shows a higher consumption of
polycarboxylates as dispersants for practical use. Neverthe-
less, polycarboxylates with a well-designed chemical struc-
ture such as PD1:3 may be efficient because better
dispersion results when they are used in the same concen-
tration as PNS.
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