CHAPTER - 4

SOLUBILITY PARAMETERS
 57

4.1 Introduction:

Concept of solubility parameter has been proved very-

useful in understanding the mechanism of solvent or carrier

49
action in the dyeing of synthetic fibres. Arieh et al.
have compared solubility parameters (SP)of different plasti­

cizing agents and aerylan filament and concluded that

plasticization action on acrylan filament is governed by polar

interactions. Ibe 154 had extended the concept to the dyeing

Qf synthetic polymer fibres with disperse dyes. Ingmells 189

found that the affinity of disperse dyes for polyester is

higher when the balance of polar and nonpolar components of

solubility parameter of dyes balance those of the polyester.

Chavan et al.147 used SP concept in the dyeing of reactive dyes

on.cotton in different solvent media. Recently Chavan et al.148

studied transfer printability of same disperse dyes on cotton

pretreated with ethylene glycols and concluded that the transfer

printability of disperse dyes can be explained on the basis of

solubility parameters concept.

In Chapter 3, mechanism of dyeing six monoazo disperse

dyes on acrylic fibre has been studied. It is proposed to

determine solubility parameters of six monoazo disperse dyes

and study the role of solubility parameters of dyes, solvent

and fibre in the dyeing process.

 58

In this chapter, some of the basic concepts of solubility

parameters including different methods of their determination

have been discussed. The procedures adopted to calculate total

solubility parameter(c/t), dispersion solubility parameter ( cfd)

and association solubility parameter ( c/a ) have been described

in detail. Correlation studies of solubility parameters and

dyeing behaviour in aqueous medium have been discussed.

An attempt is made to explain the experimental dye

adsorption results in aqueous medium. With solubility parameters

of dyes and acrylic fibres in aqueous medium.

4.2 Solubility Parameter and its determination;

A property often used as measure Of strength of interaction:

between the molecules of a compound is a cohesive energy density.

All molecules in a liquid possess^ a potential energy E, which

is equal in magnitude (but opposite in sign) to the energy required

to seperate the molecules by an infinite distance. It originates

in the attractions between molecules and, for the liquid state, it

is overcome by evaporation, because during evaporation the

potential energy of individual molecules is reduced to zero. The
£
cohesive energy is expressed as - — , where V is the molar volume,
and is numerically equal to the potential energy per cm 3 of materic

The energy required to seperate molecules in this way may

be determined experimentally from the heat of vaporization of the

 r»

liquid, Hv, which compensate for both the potential energy

change and the work done in the expansion. For one molecule

of a vapour obeying the ideal gas laws, the latter is equal to

RT; therefore :

AH - RT
Cohesive energy Density = --------- ...(1)
v

It is convenient for experimental purposes to represent the

cohesive energy density in terms of the solxjbility parameter (cf)
where cf = C.E.D. Thus the cohesive energy density can be

measured for all compounds which can be vaporized. Obviously,

Xj can not be measured in this way for polymers and dyes but

the indirect methods of assessment are possible.

The importance of solubility parameter (3P) lies in

predicting whether or not two substances will mix. When two

substances are mixed to form a solution, the potential energy

of each molecular species will be changed by the change in the

nature of new surrounding molecules. The greater the difference

between the potential energies of the two species, the greater

will be the potential energy change on mixing. The latter is

compensated by the heat of mixing. In thermodyanamic terms,

two coirponents will mix only if the free energy decreases as

a result, and the following equation must be satisfied:

A G = A Hm - T A 5m ... (2)
 where, AG = free energy change of mixing

AHm= enthalpy change of mixing

ASm= entropy change on mixing.

The entropy term is a measure of the disorderness and the

freedom of motion of molecules. Mixing tends to produce

conditions under which there is greater randomness of arran­

gement and molecular motion. Entropy change that occurs when

two components mix is therefore always positive. In real

system Hm is usually positive, so the best mixing conditions

will occur when Hm reaches a minimum value.

Hilddbrand^“*2 has attempted to express this heat of

mixing in terms of solubility parameters of the two components

by means of the following equation:

A Hm = VA ( <f A - (f B )2 VB2 ... (3)

where VA and VB are the molar fractions of the

two components.

Inspection of equation (3) reveals that Hm will be

at a minimum when the solubility parameters of the two components

are equal. Although this equation was first intended for
predicting the ease of mixing^ of liquids, its use has since

been extended to mixtures of amorphous or semicrystalline

polymers and liquids or dyebath additives.

 Cl

4.2.1 Three dimensional Solubility Parameter:

The cohesive energy density and solubility parameter

concepts were originally developed for interaction by dispersion

(London) forces alone. Later the contribution of permanent

dipoles, dipole induced dipoles and hydrogen bonding were

155 156
included to give SP a three dimensional parameter * as

follows:

c/t2 = cfd2 + cfh2 + efp2 ...(4)

where, afd = solubility parameter representing the

contribution of London dispersion forces to the cohesive energy

density, h = solubility parameter representing the contribution

Df hydrogen bonding forces to CED and cfp= solubility parameter

representing the contribution of dipole-dipole and dipole induced

dipole forces to the cohesive energy density. The sum of the

last two contributions may be defined by

da2 (5)

and represents the contribution of both polarity and the

presence of hydrogen bonding on the cohesive energy density. It

154 155
is suggested and confirmed by Ibe and others ' that for

optimum solubility (maximum swelling) not only the SP values of

polymer and solvent, but also their polarities shoiild match.

4.2.2 Determination of solubility parameter ( </t)of polymers

and dyes:

4.2.2.1 Solubility parameters of polymers:

There are several methods published for determination of

solubility parameters of polymers and dyes from physical
158 158
constants e.g. from heat of vaporization , surface tension ,

thermal coefficient 159 , Vangair

\ ■ Waals gas constants 159 , critical

pressure1153 , reduced volume and characteristic pressure1151

and group molar attraction constants . Polymers are not

volatile as solvents hence it is not possible to determine their
S values directly from AH, as can be done for the liquids.

The only v/ay to determine the solubility parameter of a polymer

experimentally is to study its interaction with the series of

solvents and assign to the polymer, the solubility parameter

value of that liquid which proves to be the best solvent. The

three experimental methods are swelling, intrinsic viscosity

and solubility of the polymers in the solvents.

The swelling or intrinsic viscosity or solubility is

measured in a series of solvents of known solubility parameter.

The solubility parameter of the polymer is then taken to be

the solubility parameter of the solvent in which the polymer

show's maximum solubility or swelling or higher viscosity

Bagda 16 3 determined the solubility parameters of polymers

using computer analysis of dispersion speed of the polymer in

solvents and solvent mixtures. He used a rotary viscometer to

determine the solution speed of polymers.

4.2.2.2 Solubility parameter of dyes;

Solubility parameter of dyes can be determined either by

 63

solubility method or from group molar attraction constants. A -

Harris*^4 obtained the solubility parameter of CFjDisperse

Violet-1 by determining the solubility of the dye in number of

solvents. Those solvents having a SP close to that of dye gave

highest solubility. Siddique 165 using Harris method determined

\ ^

\ SP 6r 'some synthesized disperse dyes. He showed that SP values

determined by solubility method matched closely with those

C determined by ^mall's method.

4.2.2.3 Determination of SP from structural formulae:

(a) Small's method;

Small 166 published a table of group - molar -attraction

constants (appendix Table-I) derived from measurements by heat of

evaporation, for calculating the solubility parameters of

compounds of known chemical structural. They can be calculated

by the following equation:

cf = f “SsF/M ...(6)

where P = density, M= molecular weight and SP, sum of the

atoms and groupings in the molecule.

(b) Hoy's Method:

Small's scheme has offered a convenient method for

estimating the SP value for many solvents and polymers. However,

167
the list of the constants is incomplete. Hoy published more
group molar attraction constants derived from measurement of
vapour pressure of a wide variety of groups. Solubility
parameter (of) is calculated from the following equation:

cf - density x £Fi /_»

molecular weight

where 5 F is the sum of the group molar attraction constants

of the compound. Hoftyzer and Vankrevelan 168 published a series

of group molar attraction constants similar to ^mall and Hoy.

(c) Van Krevelen's method:

Van Krevelen 169 derived Fi values for the contributions

of atoms i.e. C, H, N, 0, halogens and constitutional effects

(such as double or trible bonds, etc.)

Solubility parameter ( ef) can be calculated using the

following equation:

Cf = —jjp ...(8)

where ^Fi is the sum of the atomic contribution and

Vm is molar volume.

(d) Konstam and Feairheller method:

Konstam et al.170 proposed an alternative method for

calculating solubility parameter and molar volume of functional

groups. In general, straight lines resulted when the solubility

parameter of a homologous series of monofunctional compounds

were plotted against the reciprocal of their molar volume.

This is equivalent to plotting solubility parameter against

 63

number of carbon atom (n). If Vm is a linear function of n.

This method is more satisfactory for calculating the SP of high

molecular weight members of a homologeous series from data on

low molecular weight members.

(e) Rheineck method:

171
Rheineck and Lin proposed a method of estimating SP

based on known values of group additive constants (i*e. Fi and Vi)

Ae h 5 A Ei*j h
(9)
Vm
I
where AE = Cohesive energy and Vm molar volume.

(f) Fedors method:

172
Fedor proposed a method of determining SP without

using the density value of the compound. This method is

supposed to be better than Small's method for two reasons:

The contribution of much larger number of functional groups

have been evaluated, and the method requires only the knowledge

of structural formula of the compound. The following equation

is used for directly determining (cf) .

^ A ei
h do)
- TAvi „
t

where Aei and Avi ar£ the additive atomic and group contribution

fcr the energy of vapourization and molar volume respectively.

 66

(g) Wolf's method:

Wolf 173 concluded that the following equation correctly

describe the variation of the solubility parameter, with chain

length for both non-polar and polar substances and that it

presents a possibility of determining solubility parameter values

for higher molecular weight homologues by extrapolation. This

is particularly helpful for polymers for which no suitable

solvents are available.

cfi =cfm (1-^) + ...(11)

where <fi = Solubility parameter

Vi = Molar volume of i
cfm = solubility parameter of middle group
c5*e = solubility parameter of end group

Ve = molar volume of end group

4.2.3 Determination of dispersion solubility parameter ( cfd) :

Hansen 174 extended the solubility parameter principle

to take into account polar and specific interactions. He

reported that the molar energy of vapourization of a liquid

include the energies arising from all modes of interaction

which holds the liquid together. He split total energy into

three components:

A Et = A Ed + A Ep + A Eh ... (12)
 «r-
or f'VmJ
Et \ 2 _ (' VmJ
Ed \2 +

2 2 2
c/t cfd + c/p

. *. c/p and c/h are due to polar forces and can be referred

as component due to association forces ( c/a) .

. .. eft 2 = od 2 + cfa 2

175 _/*
Brown et al. determined ad from homomorph concept

(homomorph of a polar molecule is a non-polar molecule having

nearly the very same size and shape as the polar molecule).

Here, the heat of vapourization AH of the homomorph is

determined experimentally and this AH is assumed to be due to

the non-polar component of the polar substance and hence

solubility parameter due to dispersion forces can be calculated.

176
Alternatively, Keller et al. recommended a more
fundamental approach based on relationship between cfd and the
177
refractive index 'n^. Koenhen and Smolders determined,

d using the following relationship:

cfd = (9.55 x n0) - 5.55 ...(14)

For colourless compounds and solvents, the refractive index

can be conveniently determined experimentally. However, in

case of coloured material like dyes, in absence of any suitable

method, the refractive index ' n^ can be calculated theoritically

 63

177
using Lorentz-Lorenz equation

2
n - 1 M
R LL ? (15)
n + 2

where M is the molecular weight and P is the density of the

coloured substance.

It is considered that the molar refraction RLL is an

additive property of the groups or elements comprising

178 179
compounds * . The molar refraction values for the large

number of functional groups are published by Goedhart

(appendix Table-I ) 180 . The graphs for which the Revalues

are not available, can be calculated by using model compounds

containing such functional groups. In case of some of the

functional groups the information on model compound is not

available, the R^ can be calculated by using alternative

181
method proposed by Schuyer et al . They proposed to evaluate

the molar refraction of condensed aromatic compounds by . ■

considering the high mobility of electrons, which are similar

to the valence electrons of metals.

4.2.4 Determination of association solubility parameter ( cfa):

In order to determine ( c/a) it is necessary to know

solubility parameter representing the contribution of hydrogen

bonding forces to the cohesive energy density ( cfh) and

solubility parameter representing the contribution of dipole-

dipole and dipole-induced dipole forces to the cohesive

energy density.
 182
Hansen and Skaarup calculated the hydrogen bonding

component of alcohol directly from the following equation;

cfh = (5000 ~ )** ... (16)

Vm

where N is the number of hydroxyl groups in the molecule and

Vm is the molar volume. Here it is assumed that 0 -OH bond

energy is 5000 Cal/mole.

183
Paruta suggested anx empirical relationship between

and the relative permittivity t which works best for hydrogen

bonded liquids.

r X 'l
I ------“I = 0.45 -t + 18.5 ... (17)
L M paJ

where <£ is in mega pascal unit.

( 1 Mfa )% = 0.4888 Cal'1 Cm“3//2

184 C
Prausnitz et al calculated the polar component Op from the

following equation:

Ae _ ^Enon polar ^Epolar ... (18)

Vm ~ ~Vm -------- + vUi------

E/Vm has been determined experimentally, cfd vras estimated.

Hansen and Skaarup 10 p calculated or p using Bottcher's

relation for estimating the contribution of the permanent dipole

to the CED of a fluid in terms of relative permittivity,

refractive index and dipole moment.

 70

Provided the total solubility of a compound ( dt) and

its dispersion solubility parameter ( dd) are known, association

solubility parameter (Cfa) can be obtained indirectly using the

equation:

( eft)2 = ( cfd)2 + { da)2

4.3. Experimental:

4.3.1 Determination of solubility parameters ( t, d, a)

of monoazo disperse dyes used for adsorption studies:

4.3.1.1 Total Solubility parameter (dt):

+
(dt) of each dye is determined by the method of Small 166

by using molar attraction constants (Fi) for appropriate groups.

(Fi) of certain groups viz. -NF^ (arom), -NOj (arom), and

-N=N- are not given in Small's Table. Fi values of these groups

are determined as illustrated below using model compounds of

known (dt) values 16 5 . The details of the calculations of (dt)

values for monoazo disperse dyes (A-F) are given in the Tables

(tl-VI).

Calculation of molar group constant of NH~, (aromatic)

Model compound : Aniline

Molecular weight : 93.13

Density : 1.02
Solubility parameter : 11.8 (Reference 159)

7/
 71

TABLE - I

Monoazo disperse dyes# their constitution, molecular

weight and density

A
Dye Constitution Molecular Density
weight (g/cm^)

A B

A Aniline -$> Aniline 197 1.130 1.170

B Aniline -> Phenol 198 1.460

C p-Nitroaniline Aniline 242 1.407 1.407

D p-Nitroaniline -^Phenol 243 1.452

E p-Anisidine -^1,3 p-Phenylene 24 2 1.199

diami ne

* A - Determined experimentally
B = From literature (Reference 165)
 TAFT., 1.1

Determination of solubility parameter ( dt) of Dye A

Dye A (Aniline —> Aniline) Molecular weight: 197

Density : 1.18

Group Molar group constant (Fi)

1 - Phenyl d> 735 735

1 - Phenyl §> 658 . 658

1 - NH^ (aromatic) @ 342 342

1 - ~N=N-(aromatic) @ -11.4 -11.4

1 - Conjugation # 30 30

S.Fi =1751.6

Solubility parameter ( c/t) (density)^ Fi____ X

Molecular weight

_ 1.180 x 1751.6
197

= 10.50
 73
TAB LB - III

Determination of solubility parameter ( dt) of dye B

Dye B (Aniline —^Phenol) Molecular weight : 198

Density :1.460
N=N OH

Groups Molar group constants ( Fi)

1 - Phenyl d> 735 735

1 - Fhenylene 0 658 658

1 - OH (aromatic) @ 170 170

1 - -N=N- (aromatic) @ -11.4 -13.4

1 - Conjugation @ 30 30

X Fi=1581.6

Solubility parameter ( eft) (density) TFi

Molecular weight

1.460 x 1581.6
198

11.66
 74

T’f-.PT,^' _ TV

Determination of solubility parameter ( eft) of Dye C

Dye C (Disperse Orange 3) Molecular weight : 242

Density :1.407
0,U N-N- NH2.

Groups Molar group constants (fi)

2 - Phenylene @ 658 1316

1 - NH^(aromatic) @34 2 342

1 - N02(aromatic) @ 287 237

1 - -N=N-(Aromatic) @ -11.4 -11.4

1 - Conjugation @ 30 30

X Fi=1963.6

Solubility parameter ( <ft) = tVleSlar vrelght

1.407 x 1963.6
242

11.41
 75

TABLE - V

Determination of solubility parameters ( eft) of Dye D

Dye D (p-Nitroaniline — Phenol) Molecular weight : 243

1.452

Groups Molar group constants (Ei)

2 - Phenylene @ 658 1316

1 - OH (aromatic) @ 170 170

1 - MO2(aromatic) @ 287 287

1 - -N=N-(aromatic)@ -11.4 - 11.4

1 - Conjugation @ 30 30

’S.Fi»1791.6

Solubility parameter ( eft) _ (density) •£ Fi

Molecular weight

1.452 x 1791.6
243

10.70
 76

.L r-vl.'l Lil* “ Vi

Determination of solubility parameter of Dye E

Dye E (p-Anisidine -Phenylene- Molecular weight : 242

diamine
Density :1.199

h3c° NHi

Groups Molar group constants(Fi)

1- Phenylene @ 658 658

1- Phenylene-H @(658-100) 558

2- NH^ (aromatic)@ 342 684

1- 0 (ether) @ 70 70

1- CH3 @ 214 214

1- -N=N-(aromatic)@-11.4 11.4
• -

1- Conjugation @ 30 30

2Fi=2202.6

Solubility parameter ( eft) _ (density) x iFi

Molecular weight

_ 1«999 x 2202.6
242

= 10.89
 77

Molar groiip constant for

-NH2 (aromatic) - x

_(density) Fi
Molecular weight

1.02 x (735 + x)
93.13

x = 342

Calculation of molar group of -N0n (aromatic)

Model compound : Nitrobenzene

Molecular weight s 123 g

Density : 1.203

Solubility parameter : 10 (Reference 159)

— (density) Fi
“ Molecular weight

1.203 x (735 + x)
10 =
123

x = 287

Calculation of molar group constant for -N=N-(aromatic)

Model compound : Azobenzene

Molecular weight . : 182

Density : 1.203

Solubility parameter : 9.84 (Reference 144)

Fi = (2 Phenyl + 1 Conjugation + 1 -N=N-)

= (1470 + 30 + x)

1500 + x
 7

(density) Fi
Molecular weight

_ 1.203 (1500 + x)
9.84 182

x = -11.4

4.3.1.2' Dispersion solubility parameter (cfd):

Dispersion solubility parameter of six monoazo disperse

dyes are determined from refractive index of dyes as per the

procedures given in Section 4.2.3. The details of the

calculations are given in the Table-VIl to XII.

Molar refraction values published by Goldheart are

taken for calculations. The R^ values, not reported in the

literature can be calculated from the model compounds.

-N=N- is not reported in the literature. It is therefore

calculated using the model compound azobenzene (trans) 176 as

follows

Model compound : Azobenzene

-Molecular weight : 182.23

Density : 1.203
Refractive index'n’: 1.6266 (Reference 176)

Molecular weight
density

(1.6266) 2 - 1 182.23
(1.6266)oz + 2 *9m
u
= 53.66
 79

TABLE - VI

Determination of dispersion solubility parameter ( £d) of Dye A

Dye A Molecular weight : 197

Density : 1.18

Groups Group contribution to molar

refraction RTUU
.

1 - Phenyl @» 25.51 25.51

1 - Phenylene 25.03 25.03

1 - (aromatic) <f> 4.89 4.89

1 - -N=N-(aromatic)@ 2,64 2.64

rli, = 58-07
Calculations
1) Refractive index (nD) of Dye A

d _ ** Molecular weight
LL 2 . 9 X density
n~ + 2 1

.. nD = 1.612
2) Dispersion solubility parameter (cTd)

cfd = 9,55 nD - 5.55

= 9.84
 BO
TABLE - VTI

Determination of dispersion solubility parameter ( c/d) of Dye B

Molecular weight : ivy

Dye B
Density : 1 # •; -

Groups Group contribution to molar

refraction R^L of dye

1 - Phenyl @ 25.51 25.51

1 - Phenylene ® 25.03 25.03

1 - OH(aromatic) @ 2.27 2.27

1 —N=N-(aromatic)® 2.64 2.64

R 55.45
LL

Calculations

1) Refractive index (nD) of the Dye B

nD 2 - 1 Molecular weight
rll ' = 2 7“ x ~
n^ + 2 Density

.. nD = 1.753

2) Dispersion solubility parameter ( c/d)

cfd = 9.55 nD - 5.55

= 9.55 x 1.753 - 5.55

= 11.24
 31

TA8LR - VIII

Determination of dispersion solubility parameter (<^d) of Dye C

Dye C Molecular vreight : 24 2

Density : 1.407

Groups Group contribution to molar

refraction RLL of Dye

2 - Fhenylene @ 25.03 50.06

1 - NH (aromatic) @
2 4.89 4.89

1 - NC
>2 (aromatic) @ 6.662 6.662

1 -N=N-(aromatic)@ 2.64 2.64

R LL 64.25

Calculations

1) Refractive index (nD) of Dye C

nD - 1 Molecular weight
R
LL nD2 + 2 density

nD = 1.669

2) Dispersion solubility parameter ( cfd)

cfd = 9.55 nj-j - 5.55

= 9.55 x 1.669 - 5.55

10.38
 82

TAB LIS - IX

Determination of dispersion solubility parameter ( cfd) of Dye D

Dye D Molecular weight : 243

Density : 1.452

Groups Group contribution to molar

refraction RT T of Dye

2 - Phenylene @ 25.03 50.06

1 - OH (aromatic) (§ 2.27 2.27

1 - NO2 (aromatic)@> 6.662 6.662

1 - -N=N-(aromatic)@2.64 2.64

Rll - 61.63

Calculations

1) Refractive index (n^) of Dye D

= nD 2 ~ 1 . Molecular weight
LL r.D2 + 2 x
Density

nD = 1.657

2) Dispersion solubility parameter ( c/d)

(tfd) = 9.55 nD - 5.55

= 9.55 x 1.657 - 5.55

10.27
 83

TABLE - X

Determination of dispersion solubility parameter ( cfd) of Dye E

Dye E Molecular weight : 242

Density : 1.199

Groups Group contribution to molar

refraction RLL of Dye

1 - Phenylene 25.03 25.03

1 - Phenylene - H 24.44
II (aromatic)

2 - NH, # 4.89 9.78

1 - 0(ether) @ 1.77 1.77

1 - CH3 @ 5.644 5.644

1 _ -N=M-(aromatic)@ 2.64 2.64

R = 69.25
LL
C.a'l dilations

1) Refractive index (nD) of Dye E

2
nQ - 1 Molecular weight
R = ■■■........... . —... V- ..... .......... ■■■................

LL 2 „ _
nQ +2 Density

.onD= 1.601

2) Dispersion solubility parameter

( cfd) = 9055 nQ - 5.55

= 9.55 x 1.601 - 5.55

9.74
 84

TABLE - XI

Determination of association solubility parameters of

monoazo disperse dyes (a-E)~

Total Dispersion Association solubility

solubility solubility parameter
Dye
parameter parameter
( eft) ( c/d) dt)2 - (c/d)2J]^

A 10.50 9.84 3.66

B 11.66 11.24 3.098

C 11.41 10.38 4.76

D 10.70 10.27 2.99

E' 10.89 9.74 4.87

 85

rll (pfrenyD 25.51 (Table-2, Annexure)

2 Rll (Phenyl) 51.02

rll (-n=n-) 53.66 - 51.02

2.64

4.3.1.3 Association solubility parameter ( cfa):

Association solubility parameter (da) of dyes are

calculated from known values of total solubility parameters

( eft) and dispersion solubility parameters of dyes using the

following equation:

( cTt)2 = ( dd)2 + ( c/k)2

The values thus calculated alongwith values of (ft and cfd are

given in the Table-XI. .

4.3.2 Density measurement of dyes:

For measurement of density of disperse dyes, the purifi

dye was thoroughly ground to obtain uniform particle size.

Nonuniform particles give inconsistant density results. After

even grinding density measurement for each dye was carried

Qut several times to confirm consistancy of the measurement,

specific gravity method using n-hexane as displacement solvent

was adopted for the measurements. The results of the density

measurements are given in the Table I.

 86

TABLE - XII

Solubility parameters ( eft.), ( cfd) , and ( da) of dyes

and acrylic fibres

Solubility parameter * Saturation

Y ..( cfd) 0‘ _
dye uptake*
n _n0.5 -1.5
Group Dye M.Wt . Cal . cm
( da) 2
( cft) ( C(d) ( da) moles/kg xl0~

A 197 10.50 9.84 3.66 7.228 143.0

I
B 198 11.66 11.24 3.098 13.163 92.1

C 24 2 11.41 10.38 4.76 4.755 42.1

II
D 243 10.70 10.27 2.99 12.806 40.1

E 242 10.89 9.74 4.87 At # 000 75.7

Acrylic
fibres ** 12.75 9.47 8.32 1.295

* Methods of determination (Section 4.3.1)

** The values of ( eft), ( cfd) and ( da) for acrylic fibre
are taken from the literature (Reference 49).

— Saturation dye uptake values (Chapter 3)

• • •
 87

TABLE - XIII

Comparison of dispersion solubility parameter values ( dd)

calculated by using the two methods

* Refractive dd values(Cal0*5 cm-1,5)

Difference
Dye No. Index Homomorph Refractive of </d
nD concept Index method values

D 1.653 9.86 10.24 + 0.38

E 1.615 9.77 9.87 + 0.10

A 1.655 9.91 10.25 + 0.34

B 1.622 9.69 9.94 + 0.24

C 1.715 10. 19 10.82 .+ 0.63

F 1.608 9.43 9.80 + 0.37

G 1.678 10.01 10.47 + 0.46

H 1.646 9.77 10.16 + 0.39

L 1.665 9.87 10.35 + 0.48
I 1.609 9.45 9.81 + 0.36

J 1.649 9.68 10.19 + 0.51

K 1.629 9.50 10.00 + 0.50

* Ref: Ingamells, W and M.N.Thomas, Textile Chemist & Colorist

Vol. 16, 1984, p.55.

4
 as

4.3.3 Saturation dye uptake of dyes:

Method of obtaining saturation dye uptake is given in

Chapter 3.

4.4 Results and Discussion:

While attempting to correlate ' solubility parameters of

154
dyes and their solubility in the synthetic polymers..,Ibe

observed that dye molecular size had-a considerable influence

on solubility of dyes in polymer. The dyes of small size have

comparatively higher solubility in the polymer irrespective of

their solubility parmeters. In view of this, five dyes having

comparable molecular size have been selected for correlation

study. These dyes have been grouped according to their molecular

size in groups I and II. Total solubility parameter (d*t),

dispersion solubility parameter (c/d) and association solubility

parameter (da) of the five dyes , calculated as per the method

described in section 4.3.1, are summerised in the Table XII

alongwith the saturation values of the dyes on acrylic fibre.

The (rft), (dd) and (da) values of acrylic fibres shown in the

table are taken from the literature . The validity of the

calculating (dd) using theoritically obtained i'ef ractiue

index values of dyes is checked in the Table XIII . The (dd)

Qf disperse dyes whose values are given in the literature

were recalculated using refractive index method. From the Table

we find that the difference between the two methods is very

rn.:rg • no! and therefore . ( cfd) values calculated using

refractive index method can be used for interpreting the dyeing

 ■39

According to solubility parameter concept, the dyes

having closer solubility parameters should show maximum

solubility in the fibre. Comparison of (eft) values of dyes

and fibre inFig. 1, however shows that the expected correlation

does not exist between the total solubility parameter values

and dyeing behaviour. In order to study the influence of

individual contribution of dispersion and association forces

involved in cohesive energy of dyes on dyeing behaviour, the

total solubility parameter of dyes are split into their dispersion

and association solubility parameters according to the equation

(eft) = («d) + ( cSa) . Dispersion solubility parameter

of dyes are determined from refractive index of dyes which

are theoritically calculated using Lorentz and Lorenz equation

as per the procedures described above. The association solubility

parameters are then calculated from the known-values of (eft) and

( cfd) using the above equation. Such division of total solubility

147 155 184
parameters is reported by many workers ' * to explain
the experimentally observed resqlts. The values of (dd) and (da)

thus calculated, and shown in the Table XII are compared with

those of acrylic fibre in Fig.2 and Fig.3.

Comparison of (<fd) values* of dyes and fibre (Fig.2)

reveals that dyes belonging to group I shows consistant

results. Dye A has closer ( cfd) value to acrylic fibres as

compared to Dye B and shows higher dye uptake (Saturation value

14 3 x 10"* moles/kg) than that of Dye B which has saturation
value 92.1 x 10“— 3 moles/kg. Dyes belong to group III however
 90

75*7

Fig—1 Correlation of total solubility parameters (eft)

of five monoo-iso disperse dyes and acrylic fibres
with saturation values of dyes (*).
 91

Fig —Z Correlation of dispersion solubility parameters

( c/d) of five monoa2o disperse dyes and acrylic
fibres with saturation values of dyes (*).
 92

Fig — 3 Correlation of association solubility parameters ( cT&)

of five monooe.o disperse dyes and acrylic fibres with
saturation values of dyes (*)
 1

93

do not show any consistant trend between (cfd) values of dyes

and fibre and the saturation dye uptakes. Comparison of ( cTa)

values of dyes and fibre in Fig.3 shows consistant trend for

dyes belonging to both groupsl and II. Dye A of Group I and

dye E of group II both have closer ( ofa) values to that of

acrylic fibre and shows maximum dye uptake in their respective

groups. Dye uptake of dyes of group I and II are found to

decrease as the ( cfa) values going away from that of acrylic

fibre.

These observations suggest that association forces

which include dipole-dipole interactions and the charge transfer

forces as envisaged in Chapter 3 play an important role in

the adsorption of these dyes on acrylic fibre. Higher absorption

of more basic disperse dyes as observed in Chapter 3 supports

this conclusion. Ingmalles reported that,in case of polyestei

though dispersion forces of cohesive energy of solvent plays

a major role in decreasing dyeing transition temperature ( ),

the relative strengths of the dispersion and association forces

on the dyeing is also important, in solvent as well as dye

adsorption. In order to assess the relative strength of

dispersion and association forces in present case, the ratio.

( rf \ ^
Y = ----— was calculated for the acrylic fibre and each dye,
( Cfa)2
The values are given in Table-xri. These values are compared

in Fig.4. The comparison reveals that a good correlation exists

between Y of dyes, fibre and saturation dye uptakes for the
 94

C^d ^
Correlation of-Y valuer ( Y= (—7-) ) of five nonoaoo
Fi9-4 CI3
disperse dyes and acrylic fibres v.i.f.b note ration valves
of dyes (*).
dyes of both group I and II. The dye stuffs E and A

having closer Y values to acrylic fibre show higher affinity

amongst the dyes in their respective groups. Similar observation

has been made by Ingamell 186 in case of dyeing of polyester

with disperse dyes. These results show that a dye will show

maximum affinity for acrylic fibre when the balance of polar

and non-polar cohesive forces associated with dye molecules

balance those of the acrylic fibre.

4.5 Conclusion:

Saturation dye uptake of five monoazo dyes on acrylic

fibres were found to be correlated with association 5P ( dTa)

of dyes and fibre. A similar trend in the saturation values

of dyes was observed when Y = ( ^ ) of dyes and fibre, were

compared. This result suggest that association forces are

important in the adsorption of disperse dyes on acrylic fibre

and balance between dispersion and association forces decide

the maximum adsorption of disperse dyes on acrylic fibres.