JOURNAL OF THE CHINESE

Article CHEMICAL SOCIETY

Synthesis and Characterization of Melamine Formaldehyde Resins for Decorative

Paper Applications

S. Ullah,a,* M. A. Bustam,a F. Ahmad,b M. Nadeem,c M. Y. Naz,d M. Sagire and A. M. Shariffa,*

a
Research Center for CO2 Capture, Department of Chemical Engineering, Universiti Teknologi PETRONAS, 31750
Tronoh, Perak, Malaysia
b
Department of Mechanical Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia
c
Petroleum Development Oman LCC, 100 Sultanate of Oman-Muscat
d
Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia
e
Department of Chemical Engineering, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia
(Received: May 19, 2014; Accepted: Aug. 1, 2014; Published Online: Oct. 24, 2014; DOI: 10.1002/jccs.201400226)

Melamine-formaldehyde (MF) resins of improved environmental compatibility were synthesized at dif-

ferent molar ratios, temperature and pH. Five molar ratios of melamine and formaldehyde: 35:65,
36.5:63.5, 38.3:61.7, 41.1:58.9 and 42.4:58.6 were used to synthesize the corresponding resins. The pre-
pared samples were characterized by using molecular weight determination viscometery, field emission
scanning electron microscopy and thermogravimetric analysis. It was noticed that the solid content in the
resin increases with an increase in pH. The maximum percentage of the solid content (51%) was obtained
for pH of 8.5 and temperature range of 95-98 oC. The refractive index of the final product was found in-
creasing with an increase of melamine concentration in the resin. A similar trend was noticed in molecular
weight of the resins with an increase in monomer yield. The maximum molecular weight of 114218 was
obtained from the sample synthesized with MF molar ratio of 42.4:58.6.

Keywords: Melamine-formaldehyde resin; TGA; Molecular weight; Decorative paper.

INTRODUCTION Amino resins are formed by reacting formaldehyde

The natural adhesives that are being used in coating with amine functional compounds like melamine, urea and
and binding industry are derived from starches, soybeans, benzoguanamine. In such formulations, the reagents are
animal waste, byproducts of meat processing, tanning in- mixed for forming thermosetting cross-linked polymers.
dustries, etc.1-5 However, these source materials may not be Formaldehyde when reacts with melamine, forms mela-
considered as good adhesives in their pure form, which re- mine-formaldehyde (MF) resin. It is a potential material for
minds us of working on alternatives. The proper chemical anti-fire and anti-water coatings. FM resin also offers good
makeup of specific materials can make them good adhe- resistance against scratches, surface roughing, ultraviolet
sives for many industrial processes including paper boxes, light, etc. It has been estimated that 95% of globally avail-
paper bags, corrugated box boards, laminated paper boards, able melamine is used in the synthesis of resins. Binding
case sealing, carton sealing, tube winding, wood binding, and lamination industries are the primary users of mela-
gummed paper, gummed tape and textile sizing.6-9 In deco- mine based resins with 49% and 30% of total production,
rative paper industry, the industrial resins are being used as respectively. The MF resin offers chemical and mechanical
binders for years. The term “industrial resins” refers to any resistance to paperboards, plywood and fiberboards. It
synthetic polymer resin made for common use. The indus- saves the hardwood and allows the use of renewable
trial resins are the synthetic polymers having good adhe- wooden feedstock.14-16 Up until now, various polymers of
sive properties, film-forming and reactivity. The synthetic this type have been produced. The most common examples
resins have many types depending upon their source chem- are melamine-formaldehyde (MF), melamine-urea-formal-
icals. The most common resins include unsaturated polyes- dehyde (MUF) and urea-formaldehyde (UF).17 In many re-
ter resins, alkyd resins, emulsion polymers, amino resins, spects, the chemistry of the formation of melamine-based
polyurethane resins, polyamide-epichlorohydrin resins, resins is very similar to that for UF resins as explained in
formaldehyde resins, etc.10-13 Fig. 1. In first step, methylol compounds are formed by

* Corresponding author. Tel: +605-368 7570; Fax: +605-365 6176; Email: azmish@petronas.com.my (A. M. Shariff)
Tel: +605-368 7610; Fax: +605-365 6176; Email: samichemist1@gmail.com (S. Ullah)

182 © 2015 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim J. Chin. Chem. Soc. 2015, 62, 182-190
 JOURNAL OF THE CHINESE
Melamine Formaldehyde Resins for Decorative Paper CHEMICAL SOCIETY

adding formaldehyde to amine groups where N—H is ef- Synthesis of MF Resin: The method used to synthesize the
fectively added across the C=O of formaldehyde. In second MF resins was adopted from Binder and Dunky, 10 Fink11 and
step, polymers are synthesized from methylol compounds Jahromi.23 Polymerization of melamine and formaldehyde at dif-
of step 1 via condensation reaction as explained in Fig. 1. ferent molar ratios was carried out in demineralized water of 0.06
The condensation reaction can involve two methylol siemens conductivity at 75 oC. The different molar quantities of
groups or one methylol group and active hydrogen atoms. melamine (ranging from 0.1 M to 0.25 M) and 1 M of formalde-
The used reaction mechanism is similar to that one for hyde were used at constant temperature of 75 oC and pH of 8.5.
production of urea-formaldehyde resins in particle board The polymerization reaction was conducted for two hours under
and medium density fiber board industry. However, the ad- constant agitation to obtain higher degree of conversion. The pH
dition of formaldehyde to amino groups of melamine is of the reaction mixture was maintained at 8.5 by use of NaOH.
faster and more complete as compared with the reaction of The final product was obtained in the form of clear, viscous and
formaldehyde with urea.18 Another important difference is transparent liquid. The end point of the reaction was checked reg-
that the condensation reaction of the hydroxyl methylated ularly by water tolerance method. Similar procedure was repeated
melamine not only occurs under acid conditions but under again and ten samples of melamine resin were synthesized with
neutral and slightly alkaline conditions as well.19,20 In addi- different monomer ratios of melamine and formaldehyde. To
tion, the products bonded with MF resins seem to be less avoid the formation of methylene or dimethylene ether bonds: the
susceptible to the release of formaldehyde than the prod- reaction of formaldehyde with melamine can take place under ei-
ucts bonded with UF resin.13,21,22
ther acidic or basic conditions. Further reaction, however, such as
The presented research work was focused on charac-
condensation of the resultant hydroxymethyl groups with either
terization of MF resins synthesized with different molar ra-
themselves or amino groups on adjacent molecules, is acid cata-
tios of melamine and formaldehyde, and determination of
lyzed. Therefore, to avoid subsequent reaction, the methylolation
morphology, molecular weight and solid content of synthe-
reaction is carried out under basic conditions. The synthesized
sized resin samples. The effect of different molar ratios on
MF resin samples were characterized further and manipulated in
solid content and application of the MF resin on decor pa-
results and discussion section.
per were also studied. The prepared resin samples were
Characterization of MF Resin: The solid contents in resin
characterized by using molecular weight determination
samples were determined by heating them in an oven. 5 g of each
viscometery, field emission scanning electron microscopy
sample was taken on an aluminum pan and placed in an oven at
(FESEM) and thermogravimetric analysis (TGA).
125 oC for four hours. The refractive index for distilled water and
resin was determined at 30 oC by Abbe Refractometer NAR-1T
EXPERIMENTAL
liquid ATAGO. The structural morphology of MF resin samples
Melamine was used as received from Fluka. Formaldehyde
was studied through FESEM technique. The molecular weights of
(37 wt% in water), NaOH and boric acid were used as received
polymer resin samples were determined by using the viscometery
from Merck. The steps taken for synthesis and characterization of
technique. A general procedure was adopted for the determination
the resins are explained in the following sections.
of molecular weights. Flow time of each dilution of polymer solu-
tion was noted using Cannon Ubbelohde viscometer. The experi-
ments were carried out at constant temperature of 27 ± 0.1 oC.
Flow time of the solvent (water) was measured by taking the
know volume of solvent in a viscometer. Three concordant read-
ings of flow time were noted and averaged to achieve the maxi-
mum accuracy in the results. The viscometer was then emptied,
dried and 10 mL of polymer solution of 8 g/10 mL of water con-
centration was taken. Again three concordant readings of flow
time were taken. The solution was then diluted to 7 mg/10 mL by
adding 1.42 mL of the solvent in the same solution and the corre-
Fig. 1. Reaction mechanism of melamine formalde- sponding flow time was noted again. Similarly, 6 mg/10 mL, 5
hyde resin. mg/10 mL, 4 mg/10 mL dilutions were made by adding 1.91, 2.67

J. Chin. Chem. Soc. 2015, 62, 182-190 © 2015 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.jccs.wiley-vch.de 183
Article Ullah et al.

and 4 mL of solvent, respectively. All solutions were made by From the flow time relative velocity (hr); the specific vis-
staking 8 mg of polymer on the basis of solid content. The corre- cosity (hsp) and ultimately the intrinsic viscosity ([h]) of the sam-
sponding viscosity average molecular weight was measured. Ma- ples were calculated. Herein, the molecular weight of the poly-
roon and Razink equation was used to determine the viscosity av- mers was also determined by using Mark Houwink equation.24
erage molecular weight as expressed in Fig. 2.
a
[h] = K[M] (5)
2 2 3
D/c = 1/2 [h] + (K1-1/3) [h] C (1)
where, [h] is the intrinsic viscosity, ‘M’ is the molecular mass of
The values of D/c were plotted against C and straight line inter-
2 the polymer, ‘K’ is the characteristics of the polymer and solvent,
ception was equal to 1/2 [h] . 2 and ‘a’ is a constant and a function of the shape of the polymer
Measurement of Relative Viscosity: Efflux time of the coil in the solution. In case of melamine formaldehyde resin the
pure solvent is given by to. The relative viscosity is the ratio of the value of ‘a’ is usually 0.6 and ‘K’ is 0.076. In this experiment, the
viscosity of the polymer solution to the viscosity of the pure sol- values of ‘K’ and ‘a’ were based on the behavior of homopoly-
vent. It was done by taking the efflux time of the polymer solution mers in the aqueous phase. The values of these constants depend
at a given concentration (we call this t) and dividing it by ‘to’ as upon the polymer solvent interactions.
explained below: TGA analysis: The thermogravimetric analyses of the syn-
thesized samples were carried out over the whole temperature
Efflux time of solution range (50-700 oC) with ramping rate of 10 oC/min. In present case,
= Relative viscosity
Efflux time of solvent TGA Q50 Perkin Elmer was serving this purpose. This character-
t ization was performed to determine the residual weight of MF
= ht (2)
to resin.
Application of the Resin on the Paper: By optimizing the
Measurement of Specific Viscosity: The specific viscos-
best yield, the resin with improved properties was impregnated on
ity was measured by taking the difference of efflux times of the
the paper (decor paper) through impregnation process. This test
solution and the pure solvent. In other words, the efflux time of
was conducted at Kashmir Lamination Board, Faisalabad-Paki-
the pure solvent ‘to’ was subtracted from the efflux time of the so-
stan. The morphology of the impregnated resin on decorative pa-
lution ‘t’ as explained below:
pers was studied through SEM images.
Efflux time of solution - Efflux time of solvent
Efflux time of solvent RESULTS AND DISCUSSION
The melamine is used as a reactive intermediate for
= Specifice viscosity (3)
the manufacturing of MF resins. The reaction conditions
Measurement of intrinsic viscosity: The intrinsic viscos-
including time, temperature, formaldehyde/melamine
ity was measured by using the equation-4:
(F/M) ratio, pH and catalyst may influence the composition
and structure of the resin that makes up the adhesive. The
[h] = hsp / c (4)
MF resin adhesive needs to be activated to give good poly-
merization to the final product. Similar to UF resin, this
usually involves lowering the pH and raising the tempera-
ture. The catalysts added to the MF resin are either acids or
acid precursors that liberate acid upon heating. Often hard-
ener such as ammonium chloride or sulfate is added which
generates hydrogen chloride or hydrogen sulfate plus am-
monia (migrates from the adhesive). In most applications,
the products are heat-cured. Although, the bonded products
show reasonable water resistance, phenol-containing res-
ins are preferred for exterior uses in the United States. Un-
Fig. 2. General viscosity average molecular weight like the UF resin adhesives, MF resins do not show degra-
plot. dation during water boiling.25,26 They do show some loss of

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 JOURNAL OF THE CHINESE
Melamine Formaldehyde Resins for Decorative Paper CHEMICAL SOCIETY

bond strength during acceleration and exterior exposure Table 1. Different molar concentrations of melamine and
tests.27,28 formaldehyde resin at 75 oC temperature and pH 8.5
The first step in MF curing is the addition of the form- Molar Conc. of Molar Conc. of % age of Solid
No. Samples
aldehyde to the melamine as shown in Fig. 1.25 Melamine is Melamine Formaldehyde Content
a good nucleophile; the addition reaction with the electro- 1 0.13 M 1M 32
philic formaldehyde occurs under most pH conditions, al- 2 0.14 M 1M 35.4
3 0.15 M 1M 38
though the reaction rate is slower at neutral pH. The mela- 4 0.16 M 1M 40
mine reacts with up to six formaldehyde groups to form two 5 0.17 M 1M 43
methylol groups on each exocyclic amine group. The mix- 6 0.18 M 1M 45
ture of hydroxyl methyl compounds then reacts by conden- 7 0.19 M 1M 46.4
8 0.20 M 1M 47.8
sation to form the resin. The addition reaction is reversible,
9 0.21 M 1M 48.4
though generally the equilibrium is far to the right side. On 10 0.22 M 1M 49.6
the other hand, the condensation reaction to form oilgo-
mers and polymers are not very reversible which is impor-
tant for the water resistance of the product and makes it dif- Table 2. Refractive index and refraction of synthesize samples
ferent from UF resin. It is evident from the dimers illustra- Molar Conc. of Refractive Refraction
Density
tion that many isomers can be produced. Considering that Melamine and Index R = n2 -1/n2 + 2 ×
d = m/v
each melamine has three amine groups, with each amine Formaldehyde (n) 1/d
group having up to two hydroxymethyl groups attached; 0.13 : 1 1.643 0.89 0.2067
formation of both methylene and bismethylene ether bridges 0.14 : 1 1.671 0.91 0.2074
0.15 : 1 1.712 0.94 0.2126
occur, and formation of dimers, trimers and higher oligo- 0.16 : 1 1.741 0.97 0.2212
mers take place. As a result, the reaction chemistry rapidly 0.17 : 1 1.762 0.99 0.2272
reaches to its highest complexity. Pizzi and Mittal have al- 0.18 : 1 1.791 1.02 0.2443
ready studied the chemistry of such reactions.25 0.19 : 1 1.844 1.05 0.2599
0.20 : 1 1.882 1.10 0.2592
Solid Content 0.21 : 1 1.927 1.14 0.2602
The solid content in the prepared samples was rang- 0.22 : 1 1.961 1.19 0.2613
ing from 32-49.6%, the extracted data has been summa-
rized in the Table 1. It was found that the solid content in-
creases with an increase in molar concentration of Mela- and Fig. 3. The intrinsic viscosity of the sample A was de-
mine in the reaction carried out at temperature of 75 oC and termined by extrapolating the graph between concentration
pH of 8.5. The solid content of 49.6% was obtained by us- and D/c2. At zero concentration, this plot gives 1/2[h]2
ing 0.22 M concentration of Melamine and 1 M formalde- which was 2600. Thus intrinsic viscosity [h] was found to
hyde. be 72.11. From intrinsic viscosity, the molecular weight
Refractive Index was calculated by applying equation (1) and it was found to
The refractive index of all prepared samples was be 44860 as expressed in Table 3 and Fig. 3. From Table 4
measured and results were summarized in Table 2. It was and Fig. 4, the measured intrinsic viscosity of sample B was
noticed that for all MF resin samples, the refractive index 103.44. From intrinsic viscosity, the molecular weight was
was ranging from 1.643-1.964. It was also observed that calculated by applying equation (1) which was found to be
the refractive index increases with an increase in melamine 78829. Similar procedure was repeated for samples C, D
concentration in the polymers. Any increase or decrease in and E and the measured intrinsic viscosities were 117.47,
refractive index was due to the presence of water content in 123.28 and 131.14, respectively. The details have been pro-
the samples. However, in the present case, an increase in re- vided in Tables 5, 6, 7 and Figs. 5, 6, 7, respectively. The
fractive index was attributed to the presence of number of molecular weights of the samples C, D and E were 96158,
trimethlol melamine molecules as given in Table 2. 103703 and 114218, respectively. The data in Table 8 re-
Molecular weight veals that the sample E has the highest molecular weight of
The molecular weight of the selected samples (having 114218 followed by sample D, C, B and A. The molar ratio
high solid content) was measured and presented in Table 3 of the monomers used in this experiment was 0.22:1, while

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Article Ullah et al.

Table 3. Dependence of the flow time, relative viscosity, specific Table 4. Dependence of the flow time, relative viscosity, specific
viscosity, D = çsp - Inçr , and D/c2 on the concentration of viscosity, D = çsp - Inçr , and D/c2 on the concentration of
the sample A the sample B
Conc. Flow time Conc. Flow time
çr çsp D = çsp-Inçr D/c2 çr çsp D = çsp - Inçr D/c2
g/mL seconds g/mL seconds
8 ´ 10-4 128.18 1.0770 0.0770 0.00300 4688 8 ´ 10-4 129.83 1.0910 0.0910 0.00390 6094
7 ´ 10-4 127.25 1.0690 0.0690 0.00190 4042 7 ´ 10-4 128.50 1.0798 0.0798 0.00299 6111
6 ´ 10-4 125.09 1.0510 0.0510 0.00120 3333 6 ´ 10-4 126.89 1.0660 0.0660 0.00210 5833
5 ´ 10-4 124.00 1.0420 0.0420 0.00084 3367 5 ´ 10-4 125.50 1.0546 0.5460 0.00140 5670
4 ´ 10-4 122.80 1.0319 0.0319 0.00046 2915 4 ´ 10-4 124.00 1.0420 0.0420 0.00850 5362

keeping other components same as used in other samples. Table 5. Dependence of the flow time, relative viscosity, specific
From these results it was clear that molecular weight in- viscosity, D = çsp - Inçr , and D/c2 on the concentration of
the sample C
creases with an increase in melamine concentration in the
polymer. The sample E was having the maximum molecu- Conc. Flow time
çr çsp D = çsp -Inçr D /c2
lar weight and solid content. g/mL seconds
Effect of Temperature 8 ´ 10-4 131.60 1.10588 0.1059 0.00523 8185
7 ´ 10-4 129.97 1.09200 0.0920 0.00390 7959
The influence of temperature variations on MF resin
6 ´ 10-4 128.30 1.07800 0.0780 0.00280 7777
at pH 8.5 is shown in Table 9 and Fig. 8, where the solid 5 ´ 10-4 126.50 1.06300 0.0630 0.00180 7524
content was found in the range of 41-51%. The MF resin 4 ´ 10-4 124.90 1.04950 0.0495 0.00110 6875

Table 6. Dependence of the flow time, relative viscosity, specific

viscosity, D = çsp -In çr , and D/c2 on the concentration of
the sample D
Conc. Flow time
çr çsp D = çsp - Inçr D/c2
g/mL seconds
8 ´ 10-4 131.90 1.1084 0.1084 0.00547 8561
7 ´ 10-4 130.16 1.0930 0.0930 0.00410 8367
6 ´ 10-4 128.56 1.0800 0.0800 0.00300 8333
5 ´ 10-4 126.80 1.0663 0.0663 0.00202 8096
4 ´ 10-4 125.00 1.0504 0.0504 0.00120 7560

Fig. 3. Dependence of D/c2 on concentration of sample

A (R-Sq = 91.4%, R-Sq(adj) = 88.5%).
formation consists of two stages: methylolation and con-
densation. In the first step of methylolation reaction, mela-
mine reacts with formaldehyde producing a series of nine
distinct methylol melamine from mono-hexamethylol mel-
amine.29 The second step of condensation reaction leads to
the formation of large number of different oligomers con-
taining methylene bridges.
The reaction was not initiating in temperature range
of 50-55 oC. It means, the lower temperature could not ini-
tiate the chemical reaction of melamine with formaldehyde
under basic condition at pH 8.5. The reaction mechanisms
and the pathways involved in the cross-linking of MF res-
Fig. 4. Dependence of D/c2 on the concentration of the ins and the resulting chemical structures are very complex.
sample B (R-Sq = 92.6%, R-Sq(adj) = 90.1%). As the temperature crossed the minimum limit 55 oC, the

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 JOURNAL OF THE CHINESE
Melamine Formaldehyde Resins for Decorative Paper CHEMICAL SOCIETY

Table 7. Dependence of the flow time, relative viscosity, specific Table 8. Dependence of Molecular weight of Melamine
viscosity, D = çsp - Inçr , and D/c2 on the concentration of Formaldehyde samples (A-E) on monomers ratios
the sample E
S.NO Sample Monomers ratio Molecular weight
Conc. Flow time
çr çsp D = çsp - Inçr D/c 2 1 A 35:65 44860
g/mL seconds 2 B 36.5:63.5 78829
8 ´ 10-4 132.11 1.11000 0.11000 0.00600 9375 3 C 38.3:.61.7 96158
7 ´ 10-4 131.01 1.10090 0.10090 0.00470 9591 4 D 41.1:58.9 103703
6 ´ 10-4 129.30 1.08600 0.08600 0.00340 9444 5 E 42.4:58.6 114218
5 ´ 10-4 127.30 1.06970 0.06970 0.00220 9107
4 ´ 10-4 125.29 1.05294 0.05294 0.00135 8454

Table 9. The effect of temperature variation on Melamine

solid content also started to increase. The maximum yield Formaldehyde resin at pH 8.5
was obtained at reaction temperature of 95-98 oC, however, Melamine Formaldehyde Temperature
% age of Solid
the reaction end point was reached at 98 oC. At the reaction content
temperature of 95-98 oC, chain extension and cross-linking 0.22 M 1M 50-55 oC No reaction
taken place to form an insoluble and infusible three-dimen- 0.22 M 1M 55-60 oC 41
0.22 M 1M 60-65 oC 43
sional network. It has been found that the higher cross-link
0.22 M 1M 65-70 oC 45
density comes with the chemically efficient melamine resin 0.22 M 1M 70-75 47
which results in highly resistive coating on decor paper. A 0.22 M 1M 75-80 48.8
highly solid polymer resin coating compositions, cross- 0.22 M 1M 80-85 49.4
0.22 M 1M 85-90 49.8
0.22 M 1M 90-95 50.2
0.22 M 1M 95-98 51
0.22 M 1M 98-100 Over the reaction

linked with melamine resins was possessing improved

inter-coat adhesion in multiple coating applications. Mela-
mine resin as a cross-linking agent for the highly solid poly-
mer resin coating composition surprisingly substantially
eliminates inter-coat adhesion failure without any negative
effects on overall coating properties and performance.
Fig. 5. Dependence of D/c2 on the concentration of the
sample C (R-Sq = 92.1%, R-Sq(adj) = 89.5%).

Fig. 6. Dependence of D/c2 on the concentration of the Fig. 7. Dependence of D/c2 on the concentration of the
sample D (R-Sq = 86.8%, R-Sq(adj) = 82.5%). sample E (R-Sq = 68.3%, R-Sq (adj) = 57.8%).

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Article Ullah et al.

Effect of pH Table 10. The effect of pH variation on Melamine Formaldehyde

The ratio of formation of two bridges during conden- Resin at Temperature 75 oC
sation reaction depends on the pH of the reaction medium. % age of Solid
Melamine Formaldehyde PH
If the pH is relatively low (7–8), methylene bridges domi- content
nate whereas, at high pH values above 9, ether bridges are 0.22 M 1M 7.0-7.6 No reaction
favored. The effect of pH variations on MF resin at molar 0.22 M 1M 7.6-8 42
0.22 M 1M 8-8.5 45
ratio of 0.22:1 and 75 oC has been presented in Table 10 and 0.22 M 1M 8.5-9 49.2
Fig. 9. The solid content was found in range of 42-50.9%. 0.22 M 1M 9-9.5 49.6
From the results it was concluded that there is no reaction 0.22 M 1M 9.5-10 50
at pH 7.0 to 7.6. It is clear form the result that the solid 0.22 M 1M 10.5-11 50.3
0.22 M 1M 11-11.5 50.6
content increases with an increase in the pH. An increase
0.22 M 1M 12-12.5 50.9
in basicity of either nitrogen leads to a decrease in stabil- 0.22 M 1M 12.5-13 Reaction over
ity of the bond. The N-C linkage in methylene ether bonds
(-NHCH2OR) was found 1000 times more stable16,30 than
the ether bond under acidic pH conditions. The stability of form.
the -N-CH2-N- linkage increases with a decrease in the ba- Morphology of MF resin
sicity of the nitrogen. Simple reaction products of formal- The FESEM of the resins for study of their surface
dehyde with primary amines are only stable in the trimeric morphology has been illustrated in Figs. 10 and 11. The ho-
mogeneous mixing of melamine with formaldehyde to
form the polymer resin was observed in the micrographs.
The uniform resin impregnation on the decor paper was
also noticed in morphological studies. FESEM images also
revealed that the agglomeration in the resin increases with
an increase in molar concentration of melamine.
Residual weight and DTGA of MF resin
The residual weight of sample E was 4.647% and
1.32% at 500 oC and 700 oC, respectively as shown in Fig.
12. The neat melamine evaporated at 371 oC, which also
shows thermal stability of the neat melamine resins up to
150 °C. The neat melamine resins started to degrade above

Fig. 8. Effect of temperature variation on MF resin at

pH 8.5.

Fig. 10. SEM micrographs of sample 9.

Fig. 11. SEM micrographs of sample 10 showed the

Fig. 9. Effect of pH variation on MF resin at 75 oC. agglomerates.

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 JOURNAL OF THE CHINESE
Melamine Formaldehyde Resins for Decorative Paper CHEMICAL SOCIETY

300 °C, but less than 10% weight loss was found. Above residual weight of 4.647% was obtained with sample E at
350 °C, the weight loss was increased markedly. This can 50 oC.
clearly be seen in the derivative of the TGA curve in Fig.
13. The major weight losses were observed in the tempera-
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