Indian Journal of Chemical Technology

Vol. 22, Jan-Mar 2015, pp. 48-55

Synthesis and application of formaldehyde free melamine glutaraldehyde

amino resin as an effective retanning agent
Rashid Saleem1, Ahmad Adnan1 & Fahim Ashraf Qureshi2*
1

Department of Chemistry, GC University, Katchery Road, Lahore 54000, Pakistan

Office of Research, Innovation and Commercialization, Comsats Institute of Information Technology,
ChakShahzad Campus, Park Road, Islamabad 45600, Pakistan.

E-mail: qureshifa@comsats.edu.pk
Received 12 June 2013; accepted 19 June 2014
Novel melamine based free formaldehyde resin using glutaraldehyde as a condensing agent rather than formaldehyde has
been synthesized under optimum conditions for use as a retanning agent. Characteristics and effects of the polymer as a
retanning agent have been investigated against conventional melamine formaldehyde resin. Tear strength, tensile strength,
elongation at break, and scanning electron microscopy (SEM) of experimental retanned leather have been studied in
comparison with commercial melamine formaldehyde retanned leather and are found to be in better performance. Effluent
emission of both retanning baths have been evaluated and found to contain less effluent load in experimental bath, thus less
impact on the environment. Glutaraldehyde alone affects dying process and produces problem in leveling of shade. In this
study, dispersing and leveled dying property of glutaraldehyde have also been improved after condensing with melamine.
Both experimental and conventional melamine resins have shown good dispersing and leveling property in dying process of
retanned leather. Structural elucidation of the experimental resin has been carried out by FTIR technique.
Keywords: Glutaraldehyde, Melamine, Retanning, Scanning Electron Microscopy

Recently, leather production with ECO friendly labels

has gained importance due to growing demands
from customers. Among harmful substances,
free formaldehyde content is the leading one.
Formaldehyde has been enlisted in carcinogens
category 3 by European Union1,2. Formaldehyde is
used in the production of syntans which causes
the finished leather to contain free formaldehyde3.
This has major constraints on such products for
use among global consumers4,5. Syntans are
manufactured primarily by condensing formalin with
naphthalene, phenol, dicyandiamide and melamine
to form polymerized condensed products having
retanning properties for different types of leather6,7.
At present, tanners have a technical challenge
to produce leather of high quality, meeting ECO
standards from skins of low quality and low grade8.
Thus, retanning, dyeing and fatliquoring require
selective chemicals with specific pH. However,
the choice of improper chemical combination
with respect to syntans produces a differential pH
across the skin making improper filling of the
collagen fibers9. Protein hydrolysates and different
combinations of tanning agents have been worked out
in retanning as fillers to open new perspectives10,11.

Ecolabelling concepts have created awareness to

produce formaldehyde free leathers. For this purpose
several investigations have been carried out to
produce leather with desired properties using syntans
based on protein hydrolysates and vegetable tannins12.
In the present work, formaldehyde was replaced
with glutaraldehyde, an industrially available
aldehyde used as protein crosslinking agent and
disinfecting agent13, so that melamine-glutaraldehyde
resin was obtained. Glutaraldehyde is relatively less
harmful than formaldehyde. LD50 value (oral, rat) for
glutaraldehyde is 1470 mg/kg14, while for
formaldehyde is 100 mg/kg15.
Glutaraldehyde has unique properties that make
it most effective protein crosslinking agent16.
Glutaraldehyde has been proposed as environmental
friendly replacement of chrome tanning to minimize
the environmental effects17 of chrome tanning.
Leather produced by oxazolidine has shrinkage
temperature similar to that of glutaraldehyde but
is less hydrophilic and less full, because of low
molecular weight of oxazolidine than glutaraldehyde
in polymerized form18. Its usage is growing due to
decline in the formaldehyde use. Glutaraldehyde
tanned leather is hydrophilic and plumpy as tanned

SALEEM et al.: SYNTHESIS OF FORMALDEHYDE FREE MELAMINE GLUTARALDEHYDE RESIN

with formaldehyde. However, the leather color is

yellow cast, which turns into orange. The orange
color causes problem in obtaining desired shade
of leathers19. There are various available aldehydes
with mono and multifunctionalities, which may be
utilized for tanning, however, only glutaraldehyde and
its various derivatives have commercial acceptance20.
In our study, glutaraldehyde has been condensed
with melamine and sulfonated with sodium sulfamate
to produce a stabilized water soluble resin that
imparts leather with very little color and has
no disturbance in dying, and also assist in leveling of
dying as well.
Experimental Section
Chemicals and apparatus

Melamine (99.8% purity, powder) was taken

from Royal DSM and was processed as received.
Technical grade glutaraldehyde (50% w/w) was
used without purification. Commercial sulfonated
melamine formaldehyde resin and sulfamic acid of
technical grade (powder, 99.8%) was also processed
as received.
Commercial Pakistani wet blue of raw buffalo
hides were used for this study and were received
from Siddique Leather Works. Commercial grade
chemicals were used for leather processing and
analytical grade chemicals were used for spent
liquors. Viscosity was determined by Brookfield
viscometer LV DVE 230 at 25C. FT-IR spectrum
of the resins was recorded by Bruker IFS 48.

49

In a three necked flask fitted with condenser, stirrer

and thermometer, 105 g water (5.83 moles), 118.92 g
sulfamic acid (1.22 moles), 97.60 g 50% strength
sodium hydroxide (1.22 moles) were mixed to form
sodium sulfamate. An amount of 51.44g melamine
(0.40 mole) was added and heated to 45C. Afterward,
326.63 g 50% strength of glutaraldehyde (1.63 moles)
was added and temperature was raised to 852C to
obtain a clear resin solution. The reaction temperature
was maintained for ten minutes and then cooled to
60C for further condensation of the resin at 60C for
30 min. The reaction mixture was allowed to cool to
room temperature after 30 min. The solid content of
the resin was about 451%. The resin, free from
formaldehyde, was spray dried to obtain a powder form
that was used in all leather retanning experiment.
Schematic route for the synthesis of sulfonated
melamine glutaraldehyde resin is given in Fig. 1.
Characterization of resin
Estimation of solid content

Solid content of liquid resin was determined by

weighing known quantity of the resin in an empty petri
dish and drying at 103-105C for one hour as per
standard procedure22. Solid contents of the product were
calculated on dried weight basis and was found 451%.

Preparation of sulfonated melamine glutaraldehyde based resin

Melamine reacts with glutaraldehyde very

rapidly and forms a crosslinked polymer that has
nearly zero water solubility. The polymer was
synthesized by condensation of amino group of
melamine with aldehyde group of glutaraldehyde in
a basic medium. Various reaction parameters were
investigated for optimization of the required polymer
reaction. Primary product of the reaction is
methylolated melamine that is converted to polymer
by further condensation. By further condensation,
the resin converts into a crosslinked insoluble resin.
The polymer was modified chemically by reaction
with sodium sulfamate which acts as a sulfonating
agent to form a soluble product, like sulfonated
melamine formaldehyde condensate21. Optimum
conditions were worked out to synthesize the stable
retanning resin.

Fig. 1Schematic route for the synthesis of sulfonated melamine

glutaraldehyde resin

50

INDIAN J. CHEM. TECHNOL., JAN-MAR 2015

Viscosity determination

Viscosity of liquid resin was determined by

Brookfield viscometer LV DVE 230 at 25C and was
found 58 cp.
Evaluation of the product as retanning agent

Retanning properties of sulfonated melamine

glutaraldehyde condensate were assessed by
comparison against leather developed by commercial
melamine formaldehyde based retanning agent.
For comparative post tanning application of control
and experimental resins, two similar buffalo wet blue
swatches were processed separately in comparison
rotating drums as below.
Chemicals were taken on the basis of shaved
weight of hide in post tanning application. Two hides,
each of 125 g were washed with cold water for
fifteen minutes in comparison rotating drums,
followed by addition of 187.5 g of water, 1.875 g of
sodium formate and 1.25 g of sodium bicarbonate to
neutralize the hides upto pH 5-5.2. After ninety
minutes mixing, water was drained out and additional
water (250 g) was added in the drum for washing
and drained after fifteen minutes. Water (125 g) was
added for retanning, dying and fatliquoring process.
Melamine glutaraldehyde based amino resin (12.5 g)
and commercial melamine formaldehyde resin
(12.5 g) were added in retanning comparative drums
and mixed for forty five minutes. Synthetic fatliquor
(5 g) was added in retanning drums and mixed
for sixty minutes. Acid dye (4 g) was added and
mixed for thirty minutes. To adjust pH upto
3.8, formic acid (1.875) was added slowly in
one hour. Water was drained off after complete
exhaustion of bath. The leather swatches were washed
with water and hooked to dry. They were conditioned
and staked.
Physical testing and hand evaluation of leathers

Samples for physical testing were obtained from

control and experimental leather as per standard
IUP method23. Samples were conditioned 804F
temperature and 652% of relative humidity for
48 hours period. Tensile strength and percentage
elongation at break of retanned leathers were
performed by Tensile testing machine (STM 566F)
by standard procedure24.
Tear strength was performed by tear testing
machine (STM 566ST) by standard procedure25
and grain strength was evaluated by lastometer as
per standard procedure26. Assessment for softness,
fullness, roundness, grain tightness, and dye leveling

properties of control and experimental leathers

were made by hand and visual examinations.
Rating of leathers for each functional property was
experienced by three persons on a scale of 0-5 points,
where higher point indicates better property.
Analysis of spent liquor

Spent liquors of post tanning from experimental

and control trials were analyzed for Total solids
(drying at 103-105C for 1.5 h) and Chemical oxygen
demand (COD) as per standard procedure27. Emission
loads per metric ton of processed wet blue of buffalo
hides were estimated by multiplying the concentration
(mg/L) with total volume of effluent (L).
Free Formaldehyde analysis in leather

Free formaldehyde content was determined

from the leather swatches by standard procedure28.
The standard procedure is specific for the
determination of released and free formaldehyde
in leathers. The method is primarily based on
colorimetric analysis.
Reflectance measurements

The basic principle is measuring the amount of

reflected light from opaque specimen surface
at wavelengths of visible spectrum as a fraction
of reflected light by white standard illuminated
identically. This is called reflectance factor.
White standard is perfect reflecting diffuser that
shows 100% reflectance at every wavelength.
Reflectance measurement of Specimens of control
and experimental leathers were determined by
Spectraflash SF 550 (Data color).
Colour measurements

Parameters for colour measurement such as L, a, b

for control and experimental dyed crust leathers were
measured using Spectraflash SF 550 (Data color). L,
is lightness difference; a and b, shows difference in
a and b values, whereas a represents red and green
axis, and b is representing yellow and blue axis.
L, a, b and C are calculated by subtracting
corresponding values of experimental leather from the
control leather.
Scanning electron microscopic analysis

Samples from control and experimental dye

crust leathers were taken from the standard position
of sampling23. Specimens of leather were cut
with uniform thickness and washed with acetone.
They were coated with 300oA thickness of gold

SALEEM et al.: SYNTHESIS OF FORMALDEHYDE FREE MELAMINE GLUTARALDEHYDE RESIN

using Ion sputtering device, Model JFC 1500, Jeol

Japan. A Jeol JSM 6490 analytical scanning electron
Microscope embedded with Energy dispersive
X-ray analyzer was used for analysis. Micrographs
of grain and cross section of fibers were obtained
by operating SEM at high vacuum and voltage of
15 KV with higher magnification levels.
Light Fastness

Resistance of color of experimental and control

dyes crust leathers to an artificial light, Xenon
arc lamp, was determined by using standard test
procedure29. Specimens of dyed crust leathers
of experimental and control leathers were exposed
to light under xenon arc lamp along with blue
wool cloths as a standard. Assessment of fastness
was carried out by comparing fading of dyed
crust leather with that of standard and rating of 1-4 is
given, where 1 represents very low light fastness
and 4 represents very high light fastness.
Results and Discussion
Melamine based amino resin was synthesized
using glutaraldehyde as a condensing agent in
replacement of formaldehyde. The required solubility
was achieved through sulfonation by sodium
sulfamate. The synthesized resin was water miscible
like commercial melamine formaldehyde resin.
The pH of solution at 10% concentration was 7.85.
As there were no such functionalities in the
synthesized resin that could be oxidized under
light so colour of dyed leather did not changed due
to good light fastness. The particular advantage
of glutaraldehyde modified resin was the absence
of formaldehyde which is considered health hazard
and carcinogen.

51

Physical characteristics of leathers

Tear and tensile strength of dyed crust leathers

were performed both along and perpendicular to
backbone line. Resulting values for each side
corresponding to along and perpendicular to backbone
and given in Table 1. Grain crack strengths for all
dyed crust leathers were carried out. Mean values
corresponding to every experiment was averaged and
results are given in Table 1. The results are showing
that all experimental results in leather have
comparable tensile strengths, % elongation at break,
tear strength and grain cracking with that of control
leathers. Increase in tensile strength and tear strength
of experimental resin is due to strong compositing
effect of non-formaldehyde melamine resin with
collagen fibers of the leather. A higher value of
% elongation of non-formaldehyde retanned leather
is due to more flexibility character of melamine
glutaraldehyde condensate as compared to melamine
formaldehyde resin.
Free formaldehyde analysis in leather

Experimental and control retanned leathers have

been evaluated for free formaldehyde by using
standard procedure and results have been given in
Table 1. There was no detectable free formaldehyde
in experimental retanned leather; while control
retanned leather contained free formaldehyde at the
rate of about 145 mg/kg. Experimental retanned
leather showed no detectable free formaldehyde
because it was synthesized without formaldehyde.

Organoleptic properties

Organoleptic properties such as fullness and

softness of leather fibers, roundness and tightness
of leather grain, and colour uniformity after dying
for control and experimental crust leathers were
comparatively visually evaluated. An average rating
to each functional property of the experiment was
given in Fig. 2. Better property was expressed
by higher number. Fullness, grain tightness and
softness of experimental retanned leather was
higher than control melamine formaldehyde retanned
leather where as roundness and color uniformity
of retanned leathers after dying were comparable in
control and experimental leathers.

Fig.2Organoleptic properties of leathers retanned with

melamine glutaraldehyde resin and commercial melamine
formaldehyde resin

INDIAN J. CHEM. TECHNOL., JAN-MAR 2015

52

Table 1Physico chemical characteristics for leathers retanned with non formaldehyde and commercial
melamine formaldehyde based retanning agents
Physicochemical properties

Tear strength (N/cm) Parallel to backbone

Leather made by using the products

Non formaldehyde
Commercial melamine
melamine resin
formaldehyde resin
500

496

Tear Strength (N/cm) Perpendicular to backbone

675

630

Distension at grain cracking (mm)

7.75

7.35

Distension at Burst (mm)

11.25

10.75

1920

1420

50

50

1720

1514

45

41

N.D
2.5

145
2.5

Tensile strength (N/cm ) parallel to backbone

% Elongation Parallel to backbone
2

Tensile strength (N/cm ) perpendicular to backbone

% Elongation perpendicular to backbone
Free formaldehyde content
Light fastness

Table 2Characteristics of waste water for commercial melamine and nonformaldehyde melamine retanned leather
Parameters

Non formaldehyde
melamine retanning

Commercial melamine formaldehyde

retanning

Chemical Oxygen Demand (ppm)

13610

15320

Total solids (ppm)

18555

20678

Volume of effluent (L/ton of shaved hide)

1385

1385

COD based emission load (kg/ton of shaved hide)

18.84

21.21

Total solids based emission load (kg/ton of shaved hide)

25.69

28.63

Spent liquor analysis

Liquid effluent generation has been one of

the major problems of the leather tanning industry.
These effluents contain large amounts of organic
matter, chlorides and sulfates. The resulting waste
water of tannery has high salinity which cannot be
easily corrected. With evolving of industry in last
few decades, there has also been a growing awareness
of need to keep environment safe. This has been
promoted by enforcement of legislations, which have
been progressively restrictive to control the wastes
and their disposal30.
The spent liquors from experimental and control
processes were collected. Total solids (TS) and
chemical oxygen demand (COD) are two parameters,
which were chosen to analyze the environmental
impact. Observed value of total solids and chemical
oxygen demand may not give direct correlation with
environmental consequences. So their values have
been converted into emission loads. Values for total
solids and chemical oxygen demand, and calculated

emission loads are given in Table 2. It has been

observed that reduction in TS and COD load has been
obtained in formaldehyde free melamine based
retanned leather.
Scanning electron microscopic analysis

Fullness of retanned leathers can be evaluated

by viewing the grain surface and cross section
of retanned leather fibers using scanning electron
microscopy. Micrographs of retanned leathers
showing grain and cross section are given in
Fig. 3. The experimental and controlled retanned
leathers show comparable compactness in fiber
structure throughout cross section representing
uniform filling of both retanning agents.
Formaldehyde free melamine based retanned leather
is showing more compactness.
Colour difference studies

Colour measurement values for experimental and

control retanned leathers are given in Table 3.
Experimental leathers show negative value of L

SALEEM et al.: SYNTHESIS OF FORMALDEHYDE FREE MELAMINE GLUTARALDEHYDE RESIN

53

Fig. 3Scanning electron micrographs of grain (X50) and cross section of fiber structure (X500). 3(a) Grain surface of experimental
leather; 3(b) Grain surface of control leather; 3(c) Fiber cross section of experimental leather; 3(d) Fiber cross section of control leather
Table 3Colour difference measurements of leathers
Commercial melamine formaldehyde based retanned leather
Illuminant
L
a
b
D65
73.59
-0.2
29.93
Non formaldehyde melamine based retanned leather
Illuminant
D65

70.26 1.37 36.08

Distinction of experimental leather

-3.33
Darker

1.57
Red

6.15
Yellow

which is showing for darker in shade. Experimental

retanned leather has over all colour difference value
of 3.33 in comparison to control leather expressing
increase of shade strength between experiment and
control leather. Both retanned leathers have uniform
shade of dye which clearly shows equal dispersing
and leveling property of resins.

Structural elucidation

Structure of powder resin was characterized

by Infra red spectrum as given in Fig. 4 using
DRS accessories 8000 by diluting with KBr in
range of 4000-500 cm-1. A broad band at 3359.84 cm-1
is attributed to NH and OH bonds of amine
and alcohols. Two signal at 2942.67 cm-1 and
2868.22 cm-1 show antisymmetric and symmetric
vibrations of methylene group. Peak at 1566.07 cm-1
indicate carbonyl functionality of the resin.
Peak at 1409.87 cm-1 present the scissoring
vibrations of the methylene group. Absorption at
1194.41cm-1 indicates stretching vibration of the
C-S and S=O functionalities of R-SO3- group
in the resin. Sharp absorption at 814.16 cm-1
shows deformative vibrations for 1, 3, 5 triazine
ring.

54

INDIAN J. CHEM. TECHNOL., JAN-MAR 2015

Fig. 4FTIR spectrum of melamine glutaraldehyde condensate

Conclusion
Environmental regulations regarding formaldehyde
are not mostly met by formaldehyde based resins
even when formaldehyde is used in minimum
concentration. Currently environmental legislations
require eliminating such products from leather
making process. In present work, it has been
possible to completely replace formaldehyde in the
synthesis of melamine resin as a retanning agent.
The condensation of melamine is made with
glutaraldehyde which is stabilized by sulfonation
through sodium sulfamate under optimum conditions.
There is no detectable free formaldehyde in
experimental retanned leather in contrast to control
leather. Melamine formaldehyde type retanning
agents can be completely replaced by this product as
observed from physicochemical properties of retanned
leathers. Tensile and tear strengths of experimental
retanned leather are better than control. Experimental
retanned leather is darker in colour in comparison
to control leather as shown by colour difference
measurement, which is also in agreement, assessed by
visually. Glutaraldehyde alone affects dying of leather
and produce uneven shade on the leather, but after
condensing with melamine, dispersing and leveling
property of glutaraldehyde based melamine resin
has been improved just like conventional melamine
formaldehyde resin. In specific, experimental
retanned leather processed with non formaldehyde

melamine based retanning agent possesses better

performance in properties than control retanned
leather.
Acknowledgements
The research was supported by Pakistan Higher
Education Commission, Government of Pakistan and
the support is gratefully acknowledged. The authors
also acknowledge Shafi Reso Chemicals, Private
Limited for providing laboratory facilities to study
application performance of formaldehyde free
melamine resin.
References
1
2
3
4
5
6
7
8
9

Binetti R, Costamagna F M & Marcello I, Istituto Superiore

di Sanita, 42 (2006) 132.
Sylwia N, aneta P & Jacek N, Central European J Chem,
11 (2013) 16.
Mohan C R, Saravanabhavan S, Thanikaivelan P, Rao J R &
Nair B U, Clean Technol Environ Policy, 10 (2008) 287.
Germann H P & Meyndt R, Formaldehyde Free Leather:
A Realistic Objective, In Processing XXVIII IULTCS
Congress, Florence, Italy, 2005.
Thanikaivelan P, Kanthimathi M, Raghav R J & Balachandran
U N, J Am Leather Chem Assoc, 97 (2002) 127.
Kleban M, J Am Leather Chem Assoc, 97 (2002) 8.
Dix J P, J Am Leather Chem Assoc, 93 (1998) 283.
Saravanabhavan S, Thanikaivelan P, Raghava R J,
Chandrasekaran B & Nair B, J Soc Leather Technol Chem,
101 (2006) 192.
Rao J R, Sreeram K J, Nair B U & Ramasami T, Some
strategies towards mitigation of pollution from tanneries:

SALEEM et al.: SYNTHESIS OF FORMALDEHYDE FREE MELAMINE GLUTARALDEHYDE RESIN

10
11
12
13
14
15
16
17
18

A Review, Advances in wastewater treatment technologies,

(Technoscience Publications, Jaipur) 1999, 135.
Cantera C, Martegani J, Esterelles G & Vergara J,
J Soc Leather Technol Chem, 86 (2002) 195.
Liqianq J, Zonglin L, Qinghua X & Yanchan L,
J Soc Leather Technol Chem, 88 (2004) 105.
Thanikaivelan P, Rammohan C, Saravanbhana S, Raghava R
J & Nair B U, J Am Leather Chem Assoc, 102 (2007) 306.
Kupec J, Charvatova K, Navratil M, Kresalek V &
Kresalkova M, J Polym Environ, 11 (2003) 93.
Sigma-Aldrich Co. Material safety data sheet (2008).
NTISNational Technical Information Service. Formerly
U.S. Clearing house for Scientific & Technical Information.
ADA125- 539 (Springfield, VA 22161), 2005.
Isabelle M, Catherine D, Michel J B & Karen C W,
Biotechniques, 37 (2004) 790.
Dipankar C, Ariful H Q & Azad M A K, Bangladesh J Sci
Ind Res, 43 (2008) 553.
Musa A E & Gasmelseeda G A, Int J Adv Indust Eng,
1 (2013) 9.

55

19 Anthony D C & Tony C, Tanning Chemistry: The Science of

Leather, edited by Tony Covington (Royal Society of
Chemistry, Cambridge UK) 2009, 331.
20 Marion K & Roy T, Conservation of Leather and Related
Materials (Elsevier) 2006, 31.
21 Yunchao H, Fansen Z, Hu Y, Chunying L, Zhaoqiang W,
Weining L & Shukai Y, J Appl Polym Sci, 56 (1995) 1523.
22 Lenore S C, Arnold E G, Andrew D E & Trussell, Standard
Methods for the Examination of Water and Wastewater, 20th
Edn, (Port City Press, Maryland) 1999, 2540.
23 IUP 2, J Soc Leather Technol Chem, 84 (2000) 303.
24 IUP 6, J Soc Leather Technol Chem, 84 (2000) 317.
25 IUP 8, J Soc Leather Technol Chem, 84 (2000) 327.
26 IUP 9, J Soc Leather Technol Chem, 1996.
27 Lenore S C, Arnold E G, Andrew D E & Trussell, Standard
Methods for the Examination of Water and Wastewater
20th Edn, (Port City Press, Maryland) 1999, 5220.
28 IUC 19, J Soc Leather Technol Chem, 86 (2003) 289.
29 IUF 402, J Soc Leather Technol Chem, (1975).
30 Gabagnou C, Herta D & Lenglart A, World leather, (2009) 10.