Synthesis and Application of Cationic Softeners

Huseini Shabbir Patanwala* & V. A. Dorugade

Institute of Chemical Technology, Mumbai

Abstract
Esterquats which are quaternary ammonium compounds having two long (C16 C18) fatty acid chains with two
weak ester linkages, represent a new generation of fabric softening agents, having replaced the dialkyldimethyl
ammonium salts (ex. DTDMAC and DSDMAC). Inclusion of ester linkages into the aliphatic chains has significantly
improved the kinetics of biodegradation of the cationic surfactants, lowering the environmental exposure levels.
This new generation of fabric softening agents combines a good environmental profile with the structural features
required for an effective fabric conditioner. The basic drawback observed in cationic softeners is their yellowing
property. Work has been has done so as to reduce this yellowing property by carrying out the esterification reaction
in presence of nitrogen atmosphere.

Key words
Cationic softeners, textile conditioners, esterquats, triethanolamine, myristic acid, palmitic acid, stearic acid.

1. Introduction more likely to produce cloudy colloidal dispersions than

Textile softeners are used to vary the handle of fabrics
(similar to filling, stiffening and weighing finishes).
They should demonstrate a positive effect on the handle
of treated textiles: many textiles require softer, smoother,
supple handle for the best sales potential. They may
also serve to improve the processability and wear
characteristics of the textiles[1].
1.1. Cationic Softeners
Cationic surfactants have been defined as materials
which dissolve or disperse in water, concentrate and
orient at interfaces and ionize in such a way that the
cation includes a hydrocarbon chain, which is
hydrophobic and contains from 8 to 25 carbon atoms[2].
1.2. Interesting advantages[2]
Cationic compounds present some interesting advantages
as textile softeners. Because of their substantivity to
textile fibres they produce a more permanent softening
effect than either anionic or nonionic compounds.
Further, they are more effective as well, since they are
effective at much lower concentration.
The alkyl chain found to be most satisfactory in
compounds prepared with lauryl (C12) chain or with
unsaturated (oleyl) carbon chain. Dialkyl chain produces
a greater total softening effect and greater efficiency
per mole than the same type of compound containing
only one long chain.
Most of the cationic softeners show strong germicidal
properties. According to bacteriologists, those cationic
compounds with shorter alkyl chains or those having
unsaturation are better bactericides than those which
are usually preferred as textile softeners. The long,
saturated alkyl groups (C16H33 -, C18H37 -) are preferred
for softening, but they reduce water solubility. However,
when the amine is quaternised, increased solubility and
greater pH stability results. The anion may be chloride,
acetate, bromide, methosulphate, phosphate, lactate, etc.
In general, the structure and composition of the cation
determines the overall effect of the molecule and the
anion affects certain physical properties.
1.3. Types of Cationic Softeners[2]
(a) Mono-Amines and their salts: The simplest
cationics are the primary, secondary and tertiary mono-
amines and their salts, formed by neutralization of the
Journal of the TEXTILE Association

softening is the saturated C18 chain (stearyl). Since it is amines usually with acetic acid.
a saturated molecule there is minimum tendency of
yellowing. The compounds containing this chain are (b) Amido Amines: amido-amines are formed by the
reaction of a fatty acid or a glyceride (fat) and a
*Correspondance should be addressed to,
Huseini Shabbir Patanwala
substituted or unsubstituted short chain polyamine.
A/504, Kaif Towers, 40/44, Tank Bunder Road,
Reay Road, Mazgaon, Mumbai 400010, India R-COOH + H2N-CH2-CH2-N-(C2H5)2 R-CONH-CH2-
E-mail : huseini_87@yahoo.com CH2-N-(C2H5)2 + H2O

183
 (c) Imidazolines: Imidazolines are formed from fatty 2. Materials and Experimental Methods
acid and polyethylene polyamine. 2.1. Materials Required
For Synthesis
(c) Aminoesters: are aminoesters prepared by reaction
CHEMICAL GRADE SOURCE
of fatty acid or acid chloride with amino alcohols like
2-propanol For synthesis Merck Specialities Pvt. Ltd.
diethanolamine or hydroethyl ethylene diamine. Hypophosphorous 30-32% LR S.D. Fine Chemical Ltd.
acid
R-COOH + HO-CH2-CH2-NH-CH2-CH2-OH R-COO- Triethanolamine LR S.D. Fine Chemical Ltd.
CH2-CH2-NH-CH2-CH2-OH + H2O Dimethyl sulphate LR S.D. Fine Chemical Ltd.
(For synthesis)
R-COOH + HO-CH 2 -CH 2-NH-CH 2 -CH 2 -NH 2
Glycine LR S.D. Fine Chemical Ltd.
RCOOCH2-CH2-NH-CH2-CH2-NH2 + H2O Stearic acid 90% Godrej Industries Ltd.
Myristic acid 99% Godrej Industries Ltd.
(e) From dicyandiamide and stearyl amine: They are
Palmitic acid - Godrej Industries Ltd.
prepared from dicyandiamide and stearyl amine
Oleic acid - -
followed by reaction with ethylene oxide to impart water Zywet P 100 - Rossari Biotech India Pvt. Ltd.
solubility to the compound.
For Application 100% Cotton fabric; 100% Polyester
1.4. Application fabric; Acetic Acid was used.
There are two principal methods of application of For Testing Methylene Blue; Zywet P 100; Chloroform;
cationic softeners Bromophenol Blue; Hydrochloric acid and Ethanol
1. Exhaustion from dilute baths were used.
2. Padding from relatively concentrated solutions
The long bath (exhaustion) process is especially suitable 2.2. Experimental Methods
because of the natural substantivity of the softeners 2.2.1. Synthesis of Softeners[4]
and is usually adopted for knitted goods, not requiring Seven different softeners were prepared by esterification
resin treatment. With thermosetting resins (urea followed by quaternisation.
formaldehyde resin), cation lubricants/softeners are a
valuable adjunct to the treatment; since, they are not Esterification
appreciably removed in the subsequent washing 0.32 moles of either A1, A2, A3, A4, A5, A6 or A7 and
operation and serve to reduce needle cutting during 0.1 mole of triethanolamine and 1ml of 30-32%
garment manufacture and generally impart improved hypophosphorous acid were introduced into a 1 litre
tear and abrasion resistance[2]. three-necked flask equipped with a stirrer, nitrogen inlet,
internal thermometer and a distillation bridge. where,
1.5. Esterquats[3] A1 Myristic Acid; A2 Palmitic Acid; A3 Stearic
Esterquats are one of the varieties of cationic surfactants. Acid; A4 Oleic Acid
Cationic surfactants are the main ingredients of fabric A5 Myristic, Palmitic and Stearic Acid in the ratio
softening formulations used worldwide. In 1977, esterquats 2:1:1
based on triethanolamine were patented for use as fabric A6 - Myristic, Palmitic and Stearic Acid in the ratio
softeners. Some important features of esterquats are: 1:2:1
They can be formulated into high active dispersion A7 - Myristic, Palmitic and Stearic Acid in the ratio
They do not cause fabric staining and pass 1:1:2
European environmental safety guidelines The reaction mixture was then heated to a temperature
They have hydrolytic stability and the softening of 160C for 4 hours. The crude acid triethanolamine
Journal of the TEXTILE Association

can be improved by adjusting dispersion pH to a
maximum of 4.
They meet test guidelines of the Organization for
Economic Corporation and Development (OECD).
v. Out of the various existing cationic molecules for
fabric softening, eaterquats are gaining superiority
because of their ecofriendly nature and excellent
biodegradability.
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ester was then cooled. Air was then passed through the
reaction mixture with continuous stirring for 15 min.
Quaternisation
A mixture of 0.05 moles of ester from esterification
step in 75ml of isopropyl alcohol was introduced into
and heated with stirring to 45C in a 1 litre three necked
flask equipped with a stirrer, dropping funnel and reflux
condenser. 0.049 moles of dimethyl sulphate were added
dropwise over a period of 2 hours. After the addition,
the mixture was stirred for another 2 hours at 60C.
The solvent was removed via distillation and unreacted
dimethyl sulphate was destroyed by addition of 0.001
mole of glycine.
Nomenclature
Softener 1 is obtained by esterification and
quaternisation of A1 i.e. Myristic Acid, Softener 2 is
the product of esterification and quaternisation of A2
i.e. Palmitic Acid, and so on and so forth, until finally
we have Softener 7 which is the esterified and
quaternized product of A7 i.e. Myristic, Palmitic and
Stearic Acid in the ratio 1:1:2
2.2.2. Application
The finish was applied by pad-dry-cure technique.
However before application emulsions of the
corresponding esterquats were prepared as per the
following recipe
Esterquat 20%
Zywet P 100 5%
Isopropyl alcohol 2%
Water Rest
The finish bath was prepared as per the following recipe
Esterquat emulsion 15gpl
Acetic acid 2gpl
The fabric was padded through above solution with
70% expression using 2dip2nip method. Cotton fabric
was then dried at 80C for 2 mins. followed by curing
at 150C for 5 mins. whereas polyester fabric was dried
at 80C for 2 mins. followed by curing at 180C for
1 min.
2.2.3. Testing
2.2.3.1. Methods for analysis of esterquat (ionic
nature)[5]
(a) Methylene blue test
First add 2 drops of a known anionic surfactant
(Zywet P 100) was added to a mixture of 5ml
methylene blue solution and 5ml of chloroform &
shaken well and left to stand until the chloroform
layer shows a blue. Then a few drops of sample
solution was shake added well and left for layers
to form. If the blue color in the chloroform layer
becomes lighter or colorless, the existence of
cationic surfactant in the sample can be confirmed.
(b) Bromophenol blue test
Bromophenol blue solution was prepared by
addition of 20ml of 0.1% bromophenol blue in
96% ethanol to a mixture of 75ml 0.2N sodium
acetate and 925ml 0.2N acetic acid. The pH of
the solution was adjusted to 3.6-3.9.
i. For the test, 2-5drops of a neutralized sample
solution was added to 10ml of bromophenol
blue solution, shaken well and the color of
the mixture observed. If a blue color is shown,
existence of a cationic surfactant is confirmed.
ii. Alternately, 1 drop of 5% sample solution
was added to a mixture of 5ml chloroform,
5ml of 0.1% bromophenol blue dilute ethanol
solution and 1 ml 6N HCl, shaken well and
the color of the chloroform layer observed. If
a yellow color appears, there is a cationic
surfactant in the sample.
2.2.3. Methods for analysis of treated fabric
(a) Assessment of bending length was
IS: 6490-1971 was used to measure Stiffness of
fabrics. Results are expressed in bending length
(to calculate flexural rigidity) and bending modulus
of fabrics.
(b) Assessment of fabric drape
IS: 8357 1977 was used to measure the drape
coefficient of fabrics.
(c) Method of assessment of whiteness and yellowness
index
2
Cut the test specimens in 10 X 5 cm , from the
fabric to be tested. In cutting the specimens,
selvedges, end pieces, and creased or folded places
shall be avoided, and specimens should be handled
as little as possible. The specimens are cut and
the whiteness and yellowness index are measured
for the unexposed specimens. For this purpose
Datacolor Tools were used to measure the CIE
Whiteness Index and D1925 Yellowness Index.
The specimens were then allowed to be exposed
to D65 light for 8 hours & again the whiteness
index and yellowness index is measured.
Journal of the TEXTILE Association
3. Results and Discussions
3.1. Ionic nature
a. Methylene blue test:
Blue color in the chloroform layer becomes lighter
b. Bromophenol blue test:
i. Mixture of sample and bromophenol blue
solution shows a blue coloration.
ii. Chloroform layer shows yellow coloration
185
 3.2. Bending length
Graph 3.1 & 3.2: Bending length of cotton samples

Graph 3.6: Drape coefficient of Polyester Samples

Graph 3.7 & 3.8: Whitness & Yellowness index for Cotton samples
Graph 3.3 & 3.4: Bending length of polyester samples
Journal of the TEXTILE Association

Graph 3.5: Drape coefficient of Cotton Samples Graph 3.9 & 3.10: Whitness & Yellowness index for Polyster samples

186

From the ionic nature tests conducted it can be said
that the esterquats are cationic in nature. Graph 3.1,
3.2, 3.3, and 3.4 shows significant decrease in
bending length as compared to the blank specimen.
A more prominent effect is observed in case of 100%
cotton. Softeners 3, 6 and 7 provide better softening
and hence a lower value of bending length.
Graph 3.5 and 3.6 also follow a similar trend. The
treated specimen shows a decrease in the drape
coefficient, much more prominent in case of 100%
cotton when compared with 100% polyester. Softener
7, a mix of myristic, palmitic and stearic acid in the
ratio 1:1:2 gives the best draping effect.
Graph 3.7 and Graph 3.6 indicates that the whiteness
index of the treated specimen reduces after exposure,
whereas, the yellowness index increases on exposure
with D65 light. Here it can be seen that softener 3
gives higher difference in the whiteness and
yellowness index, in other words gives higher
yellowing property. Also it can be seen that softener
7 shows lowest yellowing tendency.
Similar effects are observed for Graph 3.9 and Graph
3.10, i.e., the whiteness index of the blank and treated
fabric reduces after exposure, whereas the yellowness
index increases on exposure with D65 light. Here we
can see that, softener 3 shows minimum yellowing
tendency, whereas softener 7 shows higher yellowing
tendency. However the changes in the whiteness and
yellowness index observed are more pronounced for
cotton fabric as compared to polyester fabric. Hence,
there is a higher tendency of yellowing observed in
cotton as compared to polyester.
4. Conclusion
Cationic softeners are preferred as compared to
anionic and nonionic softeners owing to their
substantivity towards textile fibres. Cationic softeners
can be applied to both, natural and synthetic fibres /
fabric. However they show a tendency of yellowing.
The above softener compositions were found to be
better for 100% cotton as compared to 100%
polyester. On comparing softener 3 and softener 4,
i.e., the one made from stearic acid and oleic acid
respectively, softener 3 gave better softness property.
Following the trends, it can be concluded that the
saturated fatty acids are more efficient for softening
when compared to unsaturated fatty acids (oleic acid
in this case). Also, longer the saturated fatty acid
chain better is the effect. In case of myristic, palmitic
and stearic acid mixtures, the softener with the three
acids in the ratio 1:1:2 i.e. softener 7 gives better
results when compared to softener 5 and 6. Hence,
it can be concluded that they work synergistically.
Also, of the seven softeners prepared, softener 3 and
softener 7 depict best results when compared to
others.
References
1. Hans-Karl Rouette, Encyclopedia of Textile Finishing,
Springer Publications, Vol. 3, p. 2114-2118 (2001).
2. V. A. Shenai, Technology of Textile Processing, Sevak
Publications, Vol. 5, p. 305-313 (2002).
3. Rashmi Tyagi, V. K. Tyagi and R. K. Khanna,
Synthesis, Characterisation and Performance of Tallow
Fatty Acids and Triethanolamine based Esterquats,
Journal of the TEXTILE Association
Journal of Oleo Science, Vol. 55, No. 7, p. 337-345
(2006).
4. Nuria Bonastre, Barbara del Valles, Joaquim Bigorra
Llosas, Sabadell, Rafael Pi Subirana, Granollers, U.
S. Patent, 5 886 201 (1999).
5. Qinguo Fan, Chemical testing of textiles, Woodhead
Publications, p. 72 (2005).
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