Documente Academic
Documente Profesional
Documente Cultură
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.
Recently, leather production with ECO friendly labels Ecolabelling concepts have created awareness to
has gained importance due to growing demands produce formaldehyde free leathers. For this purpose
from customers. Among harmful substances, several investigations have been carried out to
free formaldehyde content is the leading one. produce leather with desired properties using syntans
Formaldehyde has been enlisted in carcinogens based on protein hydrolysates and vegetable tannins12.
category 3 by European Union1,2. Formaldehyde is In the present work, formaldehyde was replaced
used in the production of syntans which causes with glutaraldehyde, an industrially available
the finished leather to contain free formaldehyde3. aldehyde used as protein crosslinking agent and
This has major constraints on such products for disinfecting agent13, so that melamine-glutaraldehyde
use among global consumers4,5. Syntans are resin was obtained. Glutaraldehyde is relatively less
manufactured primarily by condensing formalin with harmful than formaldehyde. LD50 value (oral, rat) for
naphthalene, phenol, dicyandiamide and melamine glutaraldehyde is 1470 mg/kg14, while for
to form polymerized condensed products having formaldehyde is 100 mg/kg15.
retanning properties for different types of leather6,7. Glutaraldehyde has unique properties that make
At present, tanners have a technical challenge it most effective protein crosslinking agent16.
to produce leather of high quality, meeting ECO Glutaraldehyde has been proposed as environmental
standards from skins of low quality and low grade8. friendly replacement of chrome tanning to minimize
Thus, retanning, dyeing and fatliquoring require the environmental effects17 of chrome tanning.
selective chemicals with specific pH. However, Leather produced by oxazolidine has shrinkage
the choice of improper chemical combination temperature similar to that of glutaraldehyde but
with respect to syntans produces a differential pH is less hydrophilic and less full, because of low
across the skin making improper filling of the molecular weight of oxazolidine than glutaraldehyde
collagen fibers9. Protein hydrolysates and different in polymerized form18. Its usage is growing due to
combinations of tanning agents have been worked out decline in the formaldehyde use. Glutaraldehyde
in retanning as fillers to open new perspectives10,11. tanned leather is hydrophilic and plumpy as tanned
SALEEM et al.: SYNTHESIS OF FORMALDEHYDE FREE MELAMINE GLUTARALDEHYDE RESIN 49
with formaldehyde. However, the leather color is In a three necked flask fitted with condenser, stirrer
yellow cast, which turns into orange. The orange and thermometer, 105 g water (5.83 moles), 118.92 g
color causes problem in obtaining desired shade sulfamic acid (1.22 moles), 97.60 g 50% strength
of leathers19. There are various available aldehydes sodium hydroxide (1.22 moles) were mixed to form
with mono and multifunctionalities, which may be sodium sulfamate. An amount of 51.44g melamine
utilized for tanning, however, only glutaraldehyde and (0.40 mole) was added and heated to 45C. Afterward,
its various derivatives have commercial acceptance20. 326.63 g 50% strength of glutaraldehyde (1.63 moles)
In our study, glutaraldehyde has been condensed was added and temperature was raised to 852C to
with melamine and sulfonated with sodium sulfamate obtain a clear resin solution. The reaction temperature
to produce a stabilized water soluble resin that was maintained for ten minutes and then cooled to
imparts leather with very little color and has 60C for further condensation of the resin at 60C for
no disturbance in dying, and also assist in leveling of 30 min. The reaction mixture was allowed to cool to
dying as well. room temperature after 30 min. The solid content of
the resin was about 451%. The resin, free from
Experimental Section formaldehyde, was spray dried to obtain a powder form
that was used in all leather retanning experiment.
Chemicals and apparatus
Schematic route for the synthesis of sulfonated
Melamine (99.8% purity, powder) was taken
melamine glutaraldehyde resin is given in Fig. 1.
from Royal DSM and was processed as received.
Technical grade glutaraldehyde (50% w/w) was Characterization of resin
used without purification. Commercial sulfonated Estimation of solid content
melamine formaldehyde resin and sulfamic acid of Solid content of liquid resin was determined by
technical grade (powder, 99.8%) was also processed weighing known quantity of the resin in an empty petri
as received. dish and drying at 103-105C for one hour as per
Commercial Pakistani wet blue of raw buffalo standard procedure22. Solid contents of the product were
hides were used for this study and were received calculated on dried weight basis and was found 451%.
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.
using Ion sputtering device, Model JFC 1500, Jeol Physical characteristics of leathers
Japan. A Jeol JSM 6490 analytical scanning electron Tear and tensile strength of dyed crust leathers
Microscope embedded with Energy dispersive were performed both along and perpendicular to
X-ray analyzer was used for analysis. Micrographs backbone line. Resulting values for each side
of grain and cross section of fibers were obtained corresponding to along and perpendicular to backbone
by operating SEM at high vacuum and voltage of and given in Table 1. Grain crack strengths for all
15 KV with higher magnification levels. dyed crust leathers were carried out. Mean values
corresponding to every experiment was averaged and
Light Fastness results are given in Table 1. The results are showing
Resistance of color of experimental and control that all experimental results in leather have
dyes crust leathers to an artificial light, Xenon comparable tensile strengths, % elongation at break,
arc lamp, was determined by using standard test tear strength and grain cracking with that of control
procedure29. Specimens of dyed crust leathers leathers. Increase in tensile strength and tear strength
of experimental and control leathers were exposed of experimental resin is due to strong compositing
to light under xenon arc lamp along with blue effect of non-formaldehyde melamine resin with
wool cloths as a standard. Assessment of fastness collagen fibers of the leather. A higher value of
was carried out by comparing fading of dyed % elongation of non-formaldehyde retanned leather
crust leather with that of standard and rating of 1-4 is is due to more flexibility character of melamine
given, where 1 represents very low light fastness glutaraldehyde condensate as compared to melamine
and 4 represents very high light fastness. formaldehyde resin.
Free formaldehyde analysis in leather
Results and Discussion Experimental and control retanned leathers have
Melamine based amino resin was synthesized been evaluated for free formaldehyde by using
using glutaraldehyde as a condensing agent in standard procedure and results have been given in
replacement of formaldehyde. The required solubility Table 1. There was no detectable free formaldehyde
was achieved through sulfonation by sodium in experimental retanned leather; while control
sulfamate. The synthesized resin was water miscible retanned leather contained free formaldehyde at the
like commercial melamine formaldehyde resin. rate of about 145 mg/kg. Experimental retanned
The pH of solution at 10% concentration was 7.85. leather showed no detectable free formaldehyde
As there were no such functionalities in the because it was synthesized without formaldehyde.
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.
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
Fig.2Organoleptic properties of leathers retanned with
of retanned leathers after dying were comparable in melamine glutaraldehyde resin and commercial melamine
control and experimental leathers. formaldehyde resin
52 INDIAN J. CHEM. TECHNOL., JAN-MAR 2015
Table 1Physico chemical characteristics for leathers retanned with non formaldehyde and commercial
melamine formaldehyde based retanning agents
Physicochemical properties Leather made by using the products
Non formaldehyde Commercial melamine
melamine resin formaldehyde resin
Table 2Characteristics of waste water for commercial melamine and nonformaldehyde melamine retanned leather
Parameters Non formaldehyde Commercial melamine formaldehyde
melamine retanning retanning
Spent liquor analysis emission loads are given in Table 2. It has been
Liquid effluent generation has been one of observed that reduction in TS and COD load has been
the major problems of the leather tanning industry. obtained in formaldehyde free melamine based
These effluents contain large amounts of organic retanned leather.
matter, chlorides and sulfates. The resulting waste
water of tannery has high salinity which cannot be Scanning electron microscopic analysis
easily corrected. With evolving of industry in last Fullness of retanned leathers can be evaluated
few decades, there has also been a growing awareness by viewing the grain surface and cross section
of need to keep environment safe. This has been of retanned leather fibers using scanning electron
promoted by enforcement of legislations, which have microscopy. Micrographs of retanned leathers
been progressively restrictive to control the wastes showing grain and cross section are given in
and their disposal30. Fig. 3. The experimental and controlled retanned
leathers show comparable compactness in fiber
The spent liquors from experimental and control
structure throughout cross section representing
processes were collected. Total solids (TS) and
uniform filling of both retanning agents.
chemical oxygen demand (COD) are two parameters,
Formaldehyde free melamine based retanned leather
which were chosen to analyze the environmental
is showing more compactness.
impact. Observed value of total solids and chemical
oxygen demand may not give direct correlation with Colour difference studies
environmental consequences. So their values have Colour measurement values for experimental and
been converted into emission loads. Values for total control retanned leathers are given in Table 3.
solids and chemical oxygen demand, and calculated 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
A Review, Advances in wastewater treatment technologies, 19 Anthony D C & Tony C, Tanning Chemistry: The Science of
(Technoscience Publications, Jaipur) 1999, 135. Leather, edited by Tony Covington (Royal Society of
10 Cantera C, Martegani J, Esterelles G & Vergara J, Chemistry, Cambridge UK) 2009, 331.
J Soc Leather Technol Chem, 86 (2002) 195. 20 Marion K & Roy T, Conservation of Leather and Related
11 Liqianq J, Zonglin L, Qinghua X & Yanchan L, Materials (Elsevier) 2006, 31.
J Soc Leather Technol Chem, 88 (2004) 105. 21 Yunchao H, Fansen Z, Hu Y, Chunying L, Zhaoqiang W,
12 Thanikaivelan P, Rammohan C, Saravanbhana S, Raghava R Weining L & Shukai Y, J Appl Polym Sci, 56 (1995) 1523.
J & Nair B U, J Am Leather Chem Assoc, 102 (2007) 306. 22 Lenore S C, Arnold E G, Andrew D E & Trussell, Standard
13 Kupec J, Charvatova K, Navratil M, Kresalek V & Methods for the Examination of Water and Wastewater, 20th
Kresalkova M, J Polym Environ, 11 (2003) 93. Edn, (Port City Press, Maryland) 1999, 2540.
14 Sigma-Aldrich Co. Material safety data sheet (2008). 23 IUP 2, J Soc Leather Technol Chem, 84 (2000) 303.
15 NTISNational Technical Information Service. Formerly 24 IUP 6, J Soc Leather Technol Chem, 84 (2000) 317.
U.S. Clearing house for Scientific & Technical Information. 25 IUP 8, J Soc Leather Technol Chem, 84 (2000) 327.
ADA125- 539 (Springfield, VA 22161), 2005. 26 IUP 9, J Soc Leather Technol Chem, 1996.
16 Isabelle M, Catherine D, Michel J B & Karen C W, 27 Lenore S C, Arnold E G, Andrew D E & Trussell, Standard
Biotechniques, 37 (2004) 790. Methods for the Examination of Water and Wastewater
17 Dipankar C, Ariful H Q & Azad M A K, Bangladesh J Sci 20th Edn, (Port City Press, Maryland) 1999, 5220.
Ind Res, 43 (2008) 553. 28 IUC 19, J Soc Leather Technol Chem, 86 (2003) 289.
18 Musa A E & Gasmelseeda G A, Int J Adv Indust Eng, 29 IUF 402, J Soc Leather Technol Chem, (1975).
1 (2013) 9. 30 Gabagnou C, Herta D & Lenglart A, World leather, (2009) 10.